Use of sulfur-containing compounds for controlling plant parasitic nematodes

ABSTRACT

This invention relates to the use of sulfur-containing compounds for the control of plant parasitic nematodes by application of the compounds directly to seeds, seed pieces or root systems.

BRIEF SUMMARY OF THE INVENTION Technical Field

This invention relates to the use of sulfurcontaining compounds for thecontrol of plant parasitic nematodes by application of the compoundsdirectly to seeds, seed pieces or roots.

BACKGROUND OF THE INVENTION

Plant parasitic nematode control is generally achieved by application ofnematicidally active compounds to soil prior to planting a crop. Thecompounds generally must be incorporated or injected into the soil priorto planting the crop, and this may result in certain crop phytotoxicityor lack of desired nematode control due to adverse environmentalfactors. A significant portion of crop damage due to parasitism bynematodes occurs during the initial 4-6 week development period.

Seed treatments and root dip treatments with known compounds have beenevaluated during recent years for nematode control. See, for example.Truelove, B. et al., J, Nematol 9:326-330 (1977) and Rodriguez-Kabana.R. et al., Nematropica 8:26-31 (1978). Various known compounds whichhave been evaluated as either seed seed piece or root dip treatmentnematicides include, for example, carbofuran, oxamyl, aldicarb, aldicarbsulfone, dimethoate, bendiocarb, thiabendazole, diflubenzuron,phenamiphos, ficam, diazinon, sumithion, thiadiazinthion, thionazin andmethomyl.

The application of nematicidal compounds directly as a seed, seed pieceor bare root dip treatment for early season crop protection has severaldistinct advantages both from an economic and environmental standpoint.By treating seeds, seed pieces or bare roots prior to planting, thenematicide is concentrated at the site of nematode attack and,therefore, much less active ingredient on a per acre basis is requiredin comparison with conventional soil application. This not only makesnematode control more economic, but also minimizes environmentaldisturbance and any adverse nontarget effects.

Accordingly, the object of this invention is to provide a method for theuse of certain sulfur-containing compounds to control plant parasiticnematodes by application of said compounds directly to seeds, seedpieces or bare root systems. This and other objects will readily becomeapparent to those skilled in the art in light of the teachings hereinset forth.

DISCLOSURE OF THE INVENTION

This invention relates to a method for protecting plants from plantparasitic nematodes which comprises applying to the locus of nematodeinfestation a plant protectant amount of a compound having the formula:##STR1## wherein R₁, R₂, X₁, X₂, a and b are as defined hereinafter.

DETAILED DESCRIPTION

As indicated above this invention relates to a method of protectingplants from plant parasitic nematodes by the application of certainsulfur-containing compounds to seeds, seed pieces or root systems of theplants. More particularly, this invention involves a method forprotecting plants from plant parasitic nematodes comprising applying tothe locus of nematode infestation a plant protectant amount of acompound having the formula: ##STR2## wherein:

R₁ and R₂ are independently a substituted or unsubstituted carbocyclicor heterocyclic ring system selected from a monocyclic aromatic ornonaromatic ring system, a bicyclic aromatic or nonaromatic ring system,and a bridged ring system which may be saturated or unsaturated in whichthe permissible substituents (Z) are the same or different and are oneor more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl,alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio,thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy,aryldialkylsilyloxy, triarylsilyloxy. foramidino, alkylsulfamido,dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy amino,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl,nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl,alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonYl, substituted aminoin which the permissible substituents are the same or different and areone or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl,haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio,alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl,polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino,polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl,aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts,phosphonic acid and derivative salts, alkoxycarbonylamino,alkylaminocarbonyloxy. dialkylaminocarbonyloxy, alkenyl,polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy,polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino,semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl,unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl,unsubstituted or substituted arylhydrazonomethyl, a hydroxy groupcondensed with a mono-, di- or polysaccharide. ##STR3##

R₁ and R₂ are independently a substituted heteroatom or substitutedcarbon atom, or a substituted or unsubstituted, branched or straightchain containing two or more carbon atoms or heteroatoms in anycombination in which the permissible substituents (Z) are the same ordifferent and are one or more hydrogen, halogen, alkylcarbonyl,alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio,polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino,alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy,foramidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl,polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl,alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano,hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy,polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl. substituted amino inwhich the permissible substituents are the same or different and are oneor two propargyl, alkoxyalkyl. alkylthioalkyl, alkyl, alkenyl,haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio,alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl,polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino,polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl,aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts,phosphonic acid and derivative salts, alkoxycarbonylamino,alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl,polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy,polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino,semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl,unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl,unsubstituted or substituted arylhydrazonomethyl, a hydroxy groupcondensed with a mono-, di- or polysaccharide, ##STR4##

X₁, X₂ and X₃ are independently a oovalent single bond a substltuted orunsubstituted heteroatom or substituted carbon atom, or a substituted orunsubstituted, branched or straight chain containing two or more carbonatoms or heteroatoms in any combination in which the permissiblesubstituents (Z) are the same or different and are one or more hydrogen,halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl,alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio,hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy,triarylsilyloxy, foramidino, alkylsulfamido, dialkylsulfamido,alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, animocarbonyl,alkylaminocarbonyl, ialkylaminocarbonyl, aminothiocarbonyl,alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano,hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy,polyhaloalkyl, polyhaloalkoxy alkoxycarbonyl, substituted amino in whichthe permissible substituents are the same or different and are one ortwo propargyl alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenylor polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl,polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl,alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino,polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl,triarylsilyl, sulfonic acid and derivative salts, phosphonic acid andderivative salts, alkoxycarbonylamino, alkylaminocarbonyloxydialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl,alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy,polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl,alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted orsubstituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted orsubstituted arylhydrazonomethyl, a hydroxy group condensed with a mono-,di- or polysaccharide, ##STR5##

X₁ and R₁, X₂ and R₂, X₃ and R₃ or R₄ and R₅ may be linked together toform a substituted or unsubstituted heterocyclic ring system which maybe saturated or unsaturated and in which the permissible substitutents(Z) are the same or different and are one or more hydrogen, halogen,alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl,alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio,hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy,triarylsilyloxy, foramidino, alkylsulfamido, dialkylsulfamido,alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl,alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano,hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy,polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino inwhich the permissible substituents are the same or different and are oneor two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl,haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio,alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl,polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino,polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl,aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts,phosphonic acid and derivative salts, alkoxycarbonylamino,alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl,polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy,polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylaminosemicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl,unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl,unsubstituted or substituted arylhydrazonomethyl, a hydroxy groupcondensed with a mono-, di- or polysaccharide, ##STR6##

a is a value of 0 to 2 and b is a value of 0 or 1 provided that when ais 1 or 2 then b is 0 and when b is 1 then a is 0;

wherein:

R₃ is a substituted or unsubstituted, carbocyclic or heterocyclic ringsystem selected from a monocyclic aromatic or nonaromatic ring system, abicyclic aromaic or nonaromatic ring system, and a bridged ring systemwhich may be saturated or unsaturated in which the permissiblesubstituents (Z) are the same or different and are one or more hydrogen,halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl,alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio,hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy,triarylsilyloxy, foramidino, alkylsulfamido, dialkylsulfamido,alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl,alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano,hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy,polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino inwhich the permissible substituents are the same or different and are oneor two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl,haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio,alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl,polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino,polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl,aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts,phosphonic acid and derivative salts, alkoxyoarbonylamino,alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl,polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy,polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino,semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl,unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl,unsubstituted or substituted arylhydrazonomethyl, a hydroxy groupcondensed with a mono-, di- or polysaccharide, ##STR7##

R₃ is a substituted heteroatom or substituted carbon atom, or asubstituted or unsubstituted, branched or straight chain containing twoor more carbon atoms or heteroatoms in any combination in which thepermissible substituents (Z) are the same or different and are one ormore hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl,alkoxycarbonylalkyl. alkoxycarbonylalkylthio, polyhaloalkenylthio,thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy,aryldialkylsilyloxy, triarylsilyloxy, foramidino, alkylsulfamido,dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy,amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl,nitro, cyano, hydroxycarbonyl and derivative salts. formamido, alkyl,alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted aminoin which the permissible substituents are the same or different and areone or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl,haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio,alkylsulfinyl, polyhaloalkylsulfinyl alkylsulfonyl,polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylaminopolyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl,aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts,phosphonic acid and derivative salts, alkoxycarbonylamino,alkylaminocarbonyloxy dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl,alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl,polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino,semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl,unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl,unsubstituted or substituted arylhydrazonomethyl, a hydroxy groupcondensed with a mono-, di- or polysaccharide, ##STR8##

Y₁ and Y₄ are independently oxygen or sulfur;

Y₂ and Y₃ are independently oxygen, sulfur, amino or a covalent bond;and

R₄ and R₅ are independently a substituted or unsubstituted alkyl,polyhaloalkyl, phenyl or benzyl in which the permissible substituents(Z) are the same or different and are one or more hydrogen, halogen,alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl,alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio,hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy,triarylsilyloxy, foramidino, alkylsulfamido, dialkylsulfamido,alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonylalkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano,hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy,polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino inwhich the permissible substituents are the same or different and are oneor two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl,haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio,alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl,polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino,polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl,aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts,phosphonic acid and derivative salts, alkoxycarbonylamino,alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl,polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy,polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino,semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl,unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl,unsubstituted or substituted arylhydrazonomethyl, a hydroxy groupcondensed with a mono-, di- or polysaccharide, ##STR9##

The alkyl-containing moieties above may contain from about 1 to about100 carbon atoms or greater, preferably from about 1 to about 30 carbonatoms, and more preferably from about 1 to about 20 carbon atoms, Thepolysaccharide moiety may contain up to about 50 carbon atoms,

Monocyclic ring systems emcompassed by R₁, R₂ and R₃ in formula 1 may berepresented by generalized formula 2 as follows: ##STR10## wherein B'₁represents a saturated or unsaturated carbon atom and A'₁ represents aring-forming chain of atoms which together with B'₁ forms a cyclicsystem containing from 0 to 3 double bonds or from 0 to 2 triple bonds,A'₁ may contain entirely from 2 to 12 carbon atoms, may contain acombination of from 1 to 11 carbon atoms and from 1 to 4 heteroatomswhich may be selected independently from N, O, S, P or otherheteroatoms, or may contain 4 ring-forming heteroatoms alone.

Ring-forming heteroatoms may in some cases bear oxygen atoms as inaromatic N-oxides and ring systems containing the sulfinyl, sulfonyl,selenoxide and phosphono moieties.

Selected carbon atoms contained in cycles formed by B'₁ and A'₁containing more than 3 ring-forming atoms may bear carbonyl,thiocarbonyl, substituted or unsubstituted imino groups or substitutedor unsubstituted methylidene groups.

The group designated as Z represents one or more substituents selectedindependently from among the group of substituents defined for Z herein.When the cycle formed by B'₁ and A'₁ contains fewer than 4 ring formingmembers. it should be a saturated carbocycle, i,e, cyclopropyl. When thecycle formed by B'₁ and A'₂ contains fewer than 5 ring-forming members,it should contain no more than 1 heteroatom.

lllustrative monocyclic ring structures which are encompassed by R₁, R₂and R₃ in formula 1 include the following: ##STR11## wherein Z is asdefined herein,.

Bicyclic ring systems encompassed by R₁, R₂ and R₃ in formula 1 may berepresented by generalized formulae 3 and 4 as follows: ##STR12##wherein B'₂ and B'₃ may be independently a saturated or unsaturatedcarbon atom or a saturated nitrogen atom, A'₂ and A'₃ independentlyrepresent the ring-forming chains of atoms described below and Zrepresents one or more substituents selected independently from amongthe group of substituents defined for Z herein. Combinations of A'₂ andA'₃ may contain in combination with either B'₁ or B'₂, but not both,from 0 to 2 double bonds. A'₂ and A'₃, independent of B'₂ and B'₃, maycontain entirely from 1 to 11 carbon atoms, may contain a combination of1 to 3 heteroatoms which may be selected independently from among N, O,S, P or other heteroatoms together with from 1 to 10 carbon atoms or maycontain from 1-3 ring-forming heteroatoms alone.

Ring-forming heteroatoms may in some cases bear oxygen atoms, as inaromatic N-oxides and ring systems containing the sulfinyl, sulfonyl,selenoxide and phosphono groups. Selected carbon atoms contained in A'₂and A'₃ may bear carbonyl, thiocarbonyl, substituted or unsubstitutedimino groups or substituted or unsubstituted methylidene groups,

In regard to structures encompassed within formulae 3 and 4, it is notedas follows:

(a) When B'₂ and B'₃ are both nitrogen, the groups A'₂ and A'₃ shouldeach contain no fewer than three ring atoms;

(b) When B'₂ but not B'₃ is nitrogen, either of A'₂ or A'₃ shouldcontain at least three ring atoms and the other at least two ring atoms;

(c) When either of groups A'₂ or A'₃ oontains fewer than three ringatoms, the other should contain at least three ring atoms and thebridgehead atoms should be saturated:

(d) When the group A'₂ or A'₃ contains a carbon atom bearing a carbonyl,thiocarbonyl, imino or methylidene group, it should together with B'₂and B'₃ form a cycle having at least four members;

(e) When a annular double bond is exocyclic to either of the two ringsrepresented in structures 3 and 4, it should be contained in a ringcontaining at least five members and be exocyclic to a ring containingat least five members: and

(f) When a group A'₂ or A'₃ is joined to the bridgehead atoms B'₁ andB'₂ by 2 double bonds, the group A'₂ or A'₃ is understood to contain onedouble bond and the bridgehead atoms are considered to be unsaturated.

It is recognized that bicyclic ring systems defined for R₁, R₂ and R₃may be spirocyclic ring systems and are not limited to the fusedbicyclic structures of formulae 3 and 4, Spirocyclic ring systems may besaturated or unsaturated carbocyclic or heterocyclic and may beindependently substituted by one or more substituents Z as definedherein.

Illustrative byciclic ring structures which are encompassed by R₁, R₂and R₃ in formula 1 included the following: ##STR13##

Bridged bicyclic structures encompassed by R₁, R₂ and R₃ in formula 1may be represented by generalized formulae 5, 6, and 7 as follows:##STR14## wherein B'₄ and B'₅ may be independently a saturated carbonatom optionally substituted by Z or a nitrogen atom, and the groups A'₄,A'₅ and A'₆ independently represent ring-forming chains of atoms whichmay contain, independently of B'₄ and B'₅, from 0-2 double bonds. Thegroups Z represent one or more substituents selected independently fromamong the groups of substituents defined for Z herein, .

The ring-forming elements of A'₄, A'₅ and A'₆ independent of B'₄ andB'₅, may contain entirely from 1-11 carbon atoms, may contain acombination of from 1-10 carbon atoms and from 1-3 heteroatoms which maybe selected independently from among N, O, S, P or other heteroatoms, ormay contain from 1-3 heteroatoms alone with the proviso that when one ofthe groups A'₄, A'₅ and A'₆ is a single heteroatom, the other two groupsshould contain two or more ring-forming atoms. A second proviso is thatwhen one or both of the groups B'₄ and B'₅ is nitrogen the groups A'₄,A'₅ and A'₆ should contain at least two saturated ring-forming atoms.

Ring-forming heteroatoms may in some cases bear oxygen atoms as in thesulfinyl, sulfonyl, selenoxide and phosphono moieties, Selected carbonatoms contaned in A'₄, A'₅ and A'₆ may bear one or more carbonyl,thiocarbonyl or substituted or unsubstituted imino groups.

Illustrative bridged bicyclic structures which are encompassed by R₁, R₂and R₃ in formula 1 include the following: ##STR15##

The substituents X₁, X₂ and X₃ may independently be an unsubstitutedheteroatom such as an oxygen or sulfur, as in carbonyl and thiocarbonylsystems. The substituents X₁, X₂, X₃, R₁, R₂ and R₃ may independently bea substituted heteroatom or carbon atom. X₁, X₂ and X₃ independently mayalso be a covalent single bond, or an array of atoms serving to join thesubstituents R₁, R₂ and R₃ respectively to the remainder of thesulfur-containing molecule. The group X₃ may be joined to thesubstituent R₃ by means of a single or double bond. Likewise, X₃ may beattached to the remainder of the sulfur-containing molecule by means ofa double or single bond, X₁, X₂, X₃, R₁, R₂ and R₃ independently may bea saturated or unsaturated, branched or straight chain of carbon atoms;a branched or straight, saturated or unsaturated chain of atomsconsisting of both carbon atoms and heteroatoms; or may be a branched orstraight saturated or unsaturated chain consisting entirely ofheteroatoms. Selected heteroatomic components of X₁, X₂, X₃, R₁, R₂ andR₃ may bear oxygen atoms as in the case of groups containing thesulfonyl, sulfinyl, N-oxide and phosphono moieties. Selectedheteroatomic components of X₁, X₂, X₃, R₁, R₂ and R₃ may bear one ormore substituents Z as defined herein, Selected carbon atomsparticipating in X₁, X₂, X₃, R₁, R₂ and R₃ may bear carbonyl,thiocarbonyl, substituted or unsubstituted imino, substituted orunsubstituted alkylidene or one or more substituents Z as definedherein.

The combinations of R₁ and X₁, R₂ and X₂, R₃ and X₃, and R₄ and R₅ maybe linked together to form a heterocyclic saturated or unsaturated ringsystem. This ring system may be part of a saturated or unsaturated,aromatic or nonaromatic, carbo- or hetero-, monoyclic or bicyclic ringsystem as illustrated hereinabove. Illustrative of suitable heteroatomsinclude oxygen, sulfur, nitrogen, silicon and phosphorous. The ringsystem can be optionally substituted with one or more of thesubstituents Z as defined herein.

Y₁ and Y₄ may independently be oxygen or sulfur, Y₂ and Y₃ mayindependently be oxygen, sulfur, amino or a covalent bond. R₄ and R₅, inaddition to being linked together to form a heterocyclic saturated orunsaturated ring system as described hereinabove, may be independentlysubstituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl inwhich the permissible substituents are as defined for Z herein.

It is readily apparent that formula 1 encompasses a wide variety ofsulfur-containing compounds as more particularly described hereinbelow.For example, U.S. Pat. No. 4,382,957, incorporated herein by reference,discloses and claims symmetrical N-substituted bis-carbamoyl sulfidecompounds which are encompassed by the above formula 1 and which may beused in the method of this invention. Such symmetrical N-substitutedbis-carbamoyl sulfide compounds can be prepared by the methods describedin U.S. Pat. No. 4,382,957, and are available from Union CarbideAgricultural Products Company, lnc. Research Triangle Park, NorthCarolina. Illustrative of the symmetrical N-substituted bis-carbamoylsulfide compounds of U.S. Pat. No. 4,382,957 which may be useful in themethod of this invention include the following:

N,N'-bis-[1-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime]sulfide(thiodicarb);

N,N'-bis-[1-Ethylthioacetaldehyde O-(N-methylcarbamoyl)-oxime]sulfide;

N,N'-bis-[1-IsopropylthioacetaldehydeO-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[1-(2-Cyanoethylthio)acetaldehydeO-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[5-Methyl-4-(O-(N-methylcarbamoyl)oximino)1,3-oxathiolane]sulfide;

N,N'-bis-[2-(O-(N-methylcarbamoyl)oximino)-1,4-dithiane]sulfide;

N,N'-bis-[4-(O-(N-methylcarbamoyl)oximino)-1,3-dithiolane]sulfide;

N,N'-bis-[5,5-dimethyl-4-(O-(N-methylcarbamoyl)oximino)-1,3-dithiolane]sulfide;

N,N'-bis-[3,5,5-trimethyl-2-(O-N-methylcarbamoyl)oximino)thiazolidin-4-one]sulfide;

N,N'-bis-[4,5,5-trimethyl-2-(O-(N-methylcarbamoyl)oximino)-thiazolidin-3-one]sulfide;

N,N'-bis-[2-(O-(N-methylcarbamoyl)oximino)-1,3-dithiolane]sulfide;

N,N'-bis-[2-cyano-2-methylpropionaldehydeO-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[2-nitro-2-methylpropionaldehydeO-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[1-Methylthio-N",N"-dimethylcarbamoylformaldehydeO-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[4-methyl-2-(O-(N-methylcarbamoyl)oximino)tetrahydro-1,4-thiazin-3-one]sulfide;

N,N'-bis-[3,3-Dimethyl-1-methylthiobutanone-2O-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[3-Methylthiobutanone-2 O-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[3-Methylsulfonylbutanolne-2O-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[2-Methylsulfonyl-2-methylpropionaldehydeO-(N-methylcarbamoyl)oxime]sulfide:

N,N'-bis-[1-Methylthiopyruvaldehyde O-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[3,3-Dimethyl-1-methylsulfonylbutanone-2O-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-1-[N-(Dimethylaminomethylene)carbamoyl]-1-methylthioformaldehydeO-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[1-Methylthio-1-ethoxycarbonylformaldehydeO-(N-methylcarbamoyl)oxime]sulfide;

N,N'-bis-[1,3,5-Oxadithiane-4 O-(N-methylcarbamoyloximino)]sulfide;

N,N'-bis-[1,3,5-Trithiane-2 O-(N-methylcarbamoyloximino)]sulfide;

N,N'-bis-3-[O-(N-methylcarbamoyl)oximino-1,4-oxathiane]sulfide;

N,N'-bis-[1-cyano-2,2-dimethylpropionaldehydeO-(N-methylcarbamoyloxime)]sulfide; and

N,N'-bis-[4-methyl-2-(O-(N-methylcarbamoyl)oximinotetrahydro-1,4-thiazine-5-one]sulfide.

U.S. Pat. No. 4,341,795, incorporated herein by reference, discloses andclaims asymmetrical N-substituted bis-carbamoyl sulfide compounds whichare encompassed by the above formula 1 and which may be used in themethod of this invention. Such asymmetrical N-substituted bis-carbamoylsulfide compounds can be prepared by the methods described in U.S. Pat.No. 4,341,795, and are available from Union Carbide AgriculturalProducts Company, Inc., Research Triangle Park, N.C. Illustraive of theasymmetrical N-substituted bis-carbamoyl sulfide compounds of U.S. Pat.No. 4,341,795 which may be useful in the method of this inventioninclude the following;

2,3-Dihydro-2,2-dimethyl-7-benzofuranylN-[N'-(n-butoxycarbonyl)-N'-methylaminosulfenyl]-N-methyl-carbamate;

S-Methyl-N-[N'-(N'-(N"-methyl-N"-(methoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate:

S-Methyl-N-[N'-(N"-methyl-N"-(ethoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

S-Methyl-N-[N'-(N"-methyl-N"-(butoxycarbonyl)aminosulfenyl-N'-methylcarbamoyloxy]thioacetimidate:

S-Methyl-N-[N'-(N"-methyl-N"-(t-butoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

S-Methyl-N-[N'-(N"-methyl-N"-(2-ethylhexyloxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

S-Methyl-N-[N"-methyl-N"-(n-dodecyloxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate:

S-Methyl-N-[N'-(N"-methyl-N'-(n-octadecyloxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

S-Methyl-N-[N'-(N"-methyl-N"-(benzyloxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate:

S-Methyl-N-[N'-(N'-methyl-N"-(2-methoxyethoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

S-Methyl-N-[N'-(N"-methyl-N"-(2-(2-methoxyethoxy)ethoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxyoxy]thioacetimidate:

S-Methyl-N-[N'-(N"-methyl-N"-(2-(2-(2-methoxyethoxy)ethoxy)ethoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyl]thioacetimidate:

S-Methyl-N-[N'-(N"-methyl-N"-(2-n-hexyloxyethoxycarbonyl)amlnosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

S-Methyl-N-[N"-methyl-N"-(2-(2-n-hexyloxyethoxy)ethoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate:

5-Methyl-4-[[O-[N-methyl-N-(N'-methyl-N'-(ethoxycarbonylaminosulfenyl)carbamoyl]oximino]]-1,3-oxathiolane;

5-Methyl-4-[[O-[N-methyl-N-(N'-methyl-N'-(n-dodecyloxycarbonylaminosulfenyl)carbamoyl]oximino]]-1,3oxathiolane;

5,5-Dimethyl-4-[[O-[N-methyl-N-(N'-methyl-N'-(t-butoxycarbonylaminosulfenyl)carbamoyl]oximino]]-1,3-dithiolane;

5,5-Dimethyl-4-[[O-[N-methyl-N-(N'-methyl-N-(n-dodecyloxycarbonylaminosulfenyl)carbamoyl]oximino]]-1,3dithiolane;

2-[[O-[N-Methyl-N-(N'-methyl-N'-(ethoxycarbonylaminosulfenyl)-carbamoyl]oximino]]-1,4-dithiane;

2-[[O-[N-Methyl-N-(N'-methyl-N'-(n-octadecyloxycarbonylaminosulfenyl)carbamoyl)oximino]]-1,4-dithiane:

S-2-Cyanoethylthio-N-[N'-(N"-methyl-N"-(ethoxycarbonyl)aminosulfenyl-N'-methylcarbamoyloxy]thioacetimidate;

S-2-Cyanoethylthio-N-[-N'-(N"-methyl-N"-(n-dodecyloxycarbonyl)-aminosulfenyl)-N'-methylcarbamyloxy]thioacetimidate:

S-Isopropyl-N-[N'-(N"-methyl-N"-(ethoxycarbonyl)aminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

S-Isopropyl-N-[N'-(N"-methyl-N"-(2-methoxyethoxycarbonylaminosulfenyl)-N'-methylcarbamoyloxy]thioacetimidate;

2,3-Dihydro-2,2-dimethyl-7-benzofuranylN-[N'-(ethoxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamate;

2,3-Dihydro-2,2-dimethyl-7-benzofuranylN-[N'(t-butoxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamate;

1-NaphthylN-methyl-N-[N'-(ethoxycarbonyl)-N'-methylaminosulfenyl]carbamate;

O-Methyl-2-isopropyl-4-[N-(N'-ethoxycarbonyl)-N'-methylaminosulfenyl)-N-methylcarbamoyloxy]carbanilate;

O-Methyl-2,6-dimethyl-4-[N-(N'-(ethoxycarbonyl)-N'-methylaminosulfenyl)-N-methylcarbamoyloxy]carbanilate;

O-[N-(N'-(2-Acetamidoethoxycarbonyl)-N'-butylaminosulfenyl)-N-methylcarbamoyl]-S-ethylacetothiolhydroximate;

O-[N-(N'-(2-Formamidopropycarbonyl)-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-cyanomethylacetothiolhydroximate;

O-[N-[N'-(2-Methoxycarbonylaminocyclohexyloxycarbonyl)-N-isopropylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate;

O-[N-[N'-(2-Methylsulfonyl-2-methylpropoxycarbonyl)-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate:

O-[N-[N'-(2-Ethylsulfinylbutoxycarbonyl)-N'-ethylaminosulfenyl)-N-ethylcarbamoyl]-S-methylacetothiolhydroximate;

O-[N-(N'-(1-naphthylmethoxycarbonyl)-N'-methylaminosulfenyl)-N-methylcarbamoyl)-S-methylacetothiolhydroximate;

O-[N-(N'-Cyclopentyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate;

O-[N-(N'-Cyclohexyloxycarbonyl-N'-methylaminosulfenyl)N-methylcarbamoyl]-S-methylacetothiolhydroximate;

O-[N-(N'-o-Chlorobenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate:

O-[N-(N'-m-Chlorobenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate;

O-[N-(N'-p-Chlorobenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate;

O-[N-(N'-o-Methoxybenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-ethylacetothiolhydroximate;

O-[N-(N'-m-Methoxybenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-propylacetothlolhydroximate;

O-[N-(N'-p-Methoxybenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-(2-cyanoethyl)acetothiolhydroximate;

O-[N-(N'-o-Nitrobenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothilhydroxime;

O-[N-(N'-m-Nitrobenzyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-isopropylacetothiolhydroximate;

O-[N-(N'-p-Nitrobenzyloxycarbonyl-N'-methylaminosulfenyl-N-methylcarbamoyl]-S-methyacetothiolhydroximate;

O-[N-(N'-Furfuryloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate;

O-[N-(N'-2-Pyridylmethyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-ethylacetothiolhydroximate;

O-[N-(N'-2-Thiophenemethyloxycarbonyl-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methylacetothiolhydroximate;

3-Chlorophenyl-N-[N'-methyl-N'-(2-chloroethoxycarbonyl)aminosulfenyl]-N-methylcarbamate;

2-IsopropoxyphenylN-[[N'-2-(N"-methylacetamido)ethoxycarbonyl]-N'-butylaminosulfenyl]]-N-methylcarbamate;

3,5-DimethylphenylN-[N'-methyl-N'-(2,2,2-trichloroethoxycarbamoyl(aminosulfenyl]-N-methylcarbamate;

3,5-Dimethyl-4-methylsulfinylphenylN-[N'-methyl-N'-(2,2,2-trichloroethoxycarbonyl)aminosulfenyl]-N-methylcarbamate;

3,5-Dimethyl-4-methylsulfonylphenylN-[N'-methyl-N'-(2-methylthioethoxycarbonyl)aminosulfenyl]-N-methylcarbamate;

3,5-Dimethyl-4-N,N-dimethylaminophenylN'-[N"-methyl-N"-(2-nitrobenzyloxycarbonyl)aminosulfenyl]-N'-methylcarbamate;

3,5-Dimethyl-4-acetamidophenylN-[N'-methyl-N'-(2-methylsulfinylethoxycarbonyl)aminosulfenyl]-N-methyl-carbamate;

3-Methyl-4-(dimethylaminoemethyleneimino)phenylN-[N'-methyl-N'-(2-methylsulfonylethoxycarbonyl)aminosulfenyl]-N-methylcarbamate;

3-Isopropyl-4-formoaminophenylN-[N'-ethyl-N'-(2-cyanoethoxycarbonyl)aminosulfenyl]-N-methylcarbamate;

3-IsopropylphenylN-[N'-methyl-N'-(2-nitroethoxycarbonyl)-aminosulfenyl]-N-methylcarbamate;

2-[N-[N'-(cyclohexyloxycarbonyl)-N'-methylaminosulfenyl]N-methylcarbamoyloxyimino]-4-methyl-1,4-tetrahydrothiazin-3-one:

2-[N-[N'-(cycopentyloxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamoyloxyimino]-1,4-tetrahydrothiazin-3-one;

O-[N-(N'-(3,4-Dichlorobenzyloxycarbonyl)-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methyl-1-(dimethylaminocarbonyl)formothiolhydroximate;

O-[N-(N'-(4-t-Butylbenzyloxycarbonyl]-N'-methylaminosulfenyl)-N-methycarbamoyl]-S-methyl-1-(methylaminocarbonyl)formothiolhydroximate;

O-[N-(N'-(3-methylthiobenzyloxycarbonyl)-N'-methylaminosulfenyl)-N-methylcarbamoyl]-S-methyl-1-(aminocarbonyl)-formothiolhydroximate;

2,6-Di-t-butyl-4-(2',2'-dicyanoethylidenyl)phenylN-[N'-methyl-N'-(cyclohexyloxycarbonyl)aminosulfenyl]-N-methylcarbamate;

O-[N-[N'-Methyl-N'-(butoxycarbonyl)aminosulfenyl]-N-methylcarbamoyl]-2-methyl-2-cyano-propionaldoxime;

O-[N-[N'-Methyl-N'-(propoxycarbonyl)aminosulfenyl]-N-methylcarbamoyl]-2-methyl-2-(methylthio)propionaldoxime;

O-[N-[N'-Methyl-N'-(ethoxycarbonyl)aminosulfenyl]-N-methylcarbamoyl)-2-methyl-2-nitro-propionaldoxime;

O-[(N-[N'-Methyl-N'-(methoxycarbonyl)aminosulfenyl]-N-methylcarbamoyl]-2-methyl-2-methylsulfinyl-propionaldoxime;

O-[N-[N'-Methyl-N'-(2-ethylhexyloxycarbonyl)amino-sulfenyl]-N-methylcarbamoyl]-2-methyl-2-methylsulfonyl-propionaldoxime;

O-[N-[N'-Methyl-N'-(n-octyloxycarbonyl)aminosulfenyl]-N-methylcarbamoyl]-2-methyl-2-formamido-propionaldoxime;

O-[N-[N'-Methyl-N'-(n-dodecyloxycarbonyl)aminosulfenyl]-N-methylcarbamoyl]-2-methyl-2-acetamido-propionaldoxime;

O-[N-(N'-Methyl-N'-(2-ethylhexyloxycarbonyl)aminosulfenyl)-N-methylcarbamoyl]-1-cyano-1-(t-butyl)-formohydroximate;

O-[N-[N'-(Butoxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamoyl]-1-(methylthio)-3,3-dimethyl-2-butanoneoxime;

O-[N'-[N'-(2-Ethylhexyloxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamoyl]-1-(methylthio)-3,3-dimethyl-2-butanoneoxime;

O-[N-[N'-(n-Octyloxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamoyl]-1-(methylsulfinyl)-3,3-dimethyl-2-butanoneoxime;

O-[N-[N'-(n-Pentoxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamoyl]-2-(methylsulfonyl)-3,3-dimethyl-2-butanoneoxime; and

O-[N-[N'-(Butoxycarbonyl)-N'-methylaminosulfenyl]-N-methylcarbamoyl]-3-(methylsulfonyl)-2-butanoneoxime.

U.S. Pat. No. 4,551,472, incorporated herein by reference, discloses andclaims unsymmetrical N-substituted bis-carbamoyl sulfide compounds whichare encompassed by the above formula 1 and which may be used in themethod of this invention. Such unsymmetrical N-substituted bis-carbamoylsulfide compounds can be prepared by the methods described in U.S. Pat.No. 4,551,472, and are available from Union Carbide AgriculturalProducts Company, Inc., Research Triangle Park, N.C. Illustrative of theunsymmetrical N-substituted bis-carbamoyl sulfide compounds of U.S. Pat.No. 4,551,472 which may be useful in the method of this inventioninclude the following:

N-[2-Methylthio-2-methylpropionaldehyde-O-(N-methylcarbamoyl)oxime]N-[1-methylthioacetaldehyde O-(N-methylcarbamoyl)oxime]sulfide;

N-[1-MethylthioacetaldehydeO-(N-methylcarbamoyl)oxime]N-[2-O-(N-methylcarbamoyl)oximino-1,4-dithiane]sulfide;

N-[1-MethylthioacetaldehydeO-(N-methylcarbamoyl)oxime]N-[2,3-dihydro-2,2,-dimethyl-7-(N-methylcarbamoyloxy)benzofuran]sulfide;

N-[1-MethylthioacetaldehydeO-(N-methylcarbamoyl)oxime]N-(3-isopropylphenyl N-methylcarbamate)sulfide;

N-[1-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime]N-(1-naphthylN-methylcarbamate) sulfide:

N-[2-Methylthio-2-methylpropionaldehydeO-(N-methylcarbamoyl)oxime]N-(1-naphthyl N-methylcarbamate) sulfide;

N-[1-MethylthioacetaldehydeO-(N-methylcarbamoyl)oxime]N-(2-isopropoxyphenyl N-methylcarbamate)sulfide;

N-[1-Methylthioacetaldehyde O-(N-methylcarbamoyl)oximeN-(4-dimethylamino-3,5-xylyl N-methylcarbamate) sulfide:

N-[2-Methylthio-2-methylpropionaldehyde O-(N-methylcarbamoyl)oxime]N-(3-isopropyl-4-methoxycarbonylaminophenyl N-methylcarbamate) sulfide;

N-[2-Methylthio-2-methylpropionaldehydeO-(N-methylcarbamoyl)-oxime[N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)benzofuran]sulfide;

N-[1-Methylthio-N',N'-dimethylcarbamoylformaldehydeO-(N-methylcarbamoyl)oxime] N-[1-methylthoacetaldedehydeO-(N-methylcarbamoyl)oxime] sulfide;

N-[2-Methylsulfonyl-2-methylpropionaldehyde O-(N-methylcarbamoyl)oxime]N-[2,3 dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)benzofuran] sulfide;

N-[2-O-(N-methylcarbamoyl)oximino-1,4-dithiane]N-(3-isopropylphenylN-methylcarbamate) sulfide;

N-[1-Methylthioacetaldehyde O-(N-methylcarbamoyl)oximeN-[4-(N',N'-dimethylformamidino)-3,5-xylyl N-methylcarbamate] sulfide;

N-[1-Methylthioacetaldehyde O-(N-methyloacbamoyl)oximeN-[(N',N'-dimethylaminomethylenecarbamoyl)-1-methylthioformaldehydeO-(N-methylcarbamoyl)oxime] sulfide;

N-[2-Methylthio-2-methylpropionaldehyde O-(N-methylcarbamoyl)oxime]N-(4-dimethylamino-3,5-xylyl N-methylcarbamate) sulfide;

N-[3,3-Dimethyl-1-methylthiobutanone-2O-(N-methylcarbamoyl)oxime]N-[1-methylthioacetaldehyde O-(N-methylcarbamoyl)oxime] sulfide;

N-[3,3-Dimethyl-1-methylsulfonylbutanone-2O-(N-methylcarbamoyl)oxime]N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)benzofuran] sulfide;

N-[3-Methylsulfonylbutanone-2 O-(N-methylcarbamoyl)oxime]N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)benzofuran] sulfide:

N-[3,3-Dimethyl-1-methylthiobutanone-2 O-(N-methylcarbamoyl)oxime]N-[1-methylthioacetaldehyde O-(N-methylcarbamoyl)oxime] sulfide;

N-[2-Cyano-2-methylpropionaldehyde O-(N-methylcarbamoyl)oxime]N-(1-naphthyl N-methylcarbamate) sulfide;

N-[1-Methylthio-N',N'-dimethylcarbamoylformaldehydeO-(N-methylcarbamoyl)oxime) N-[2,3-dihydro2,2-dimethyl-7-(N-methylcarbamoyloxy)benzofuran] sulfide;

N-[1-Methylthiopyruvaldehyde O-(N-methylcarbamoyl)oxime]N-[1-methylthioacetaldehyde O-(N-methylcarbamoyl) oxime] sulfide;

N-[2-O-(N-methylcarbamoyl)oximino-1,3-dithiolane]N-(1-naphthylN-methylcarbamate) sulfide;

N-[5-Methyl-4 O-(N-methylcarbamoyl)oximino-1,3-dithiolane] N-(1-naphthylN-methylcarbamate) sulfide;

N-[1-(2-cyanoethylthio)acetaldehyde O-(N-methylcarbamoyl) oxime]N-(1-naphthyl N-methylcarbamate) sulfide;

N-[1-(2-cyanoethylthio)acetaldehyde O-(N-methylcarbamoyl)oxime]N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)benzofuran] sulfide;

N-[4,5,5-Trimethyl-2 O-(N-methylcarbamoyl)oximinothiazolidin-3-one]N-[1-methylthioacetaldehyde O-(N-methylcarbamoyl)oxime] sulfide;

N-[4,5,5-Trimethyl-2O-(N-methylcarbamoyl)oximinothiazolidin-3-one[N-[3,5,5-trimethyl-2O-(N-methylcarbamoyl)oximinothiazolidin-4-one] sulfide;

N-[4-Methyl-2,O-(N-methylcarbamoyl)oximino-tetrahydro-1,4-thiazine-3-one]N-(1-naphthylN-methylcarbamate) sulfide;

N-[4-Methyl-2O-(N-methylcarbamoyl)oximino-tetrahydro-1,4-thiazine-3-one]N-[1-(2-cyanoethylthio)acetaldehyde O-(N-methylcarbamoyl)oxime]sulfide;

N-[4-Methyl-2O-(N-methylcarbamoyl)oximino-tetrahydro-1,4-thiazine-3-onejN-[1-methylthioacetaldehyde O-(N-methylcarbamoyl)oxime sulfide;

N-[5,5-Dimethyl-4 O-(N-methylcarbamoyl)oximino1,3-dithiolane]N-(1-naphthyl N-methylcarbamate) sulfide;

N-[2-(O-(N-methylcarbamoyl)oximino-4,4-dithiane]N-[4-dimethylamino-3,5-xylylN-methylcarbamate] sulfide;

N-[2-(O-(N-methylcarbamoyl)oximino-1,4-dithiane]N-[3-isopropyl-4-methoxycarbonylamino-(N-methylcarbamoyloxy)benzene]sulfide;

N-[1-(2-cyanoethylthio)acetaldehyde O-(N-methylcarbamoyl)oxime]N-[2-(2-dithiolanyl) phenyl N-methyl carbamate] sulfide;

N-[1-(2-cyanoethylthio)acetaldehyde O-(N-methylcarbamoyl)oxime]N-[2-(2-dioxalanyl) phenyl-N-methylcarbamate] sulfide;

N-[1-isopropylthioacetaldehyde O-(N-methylcarbamoyl)oxime]N-(2-propynyloxy phenyl N-methylcarbamate] sulfide;

N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamate]N-[propynyl N-methyl carbamate] sulfide;

N-[1-(2-cyanoethylthio) acetaldehyde O-(N-methylcarbamoyl)oxime]N-[4-phenoxyphenyl N-methylcarbamate] sulfide;

N-[1-Methylthio-N',N'-dimethylcarbamoylformaldehydeO-(N-methylcarbamoyl)oxime] N-[2-(2-dithiolanyl) phenylN-methylcarbamate] sulfide;

N-[1-(2-cyanoethylthioacetaldehyde O-[N-methylcarbamoyl)oxime]N-[2-isopropoxyphenyl N-methylcarbamate] sulfide;

N-[2-O-(N-methylcarbamoyl)oximino-1,3,5-trithiane] N-[2-isopropoxyphenylN-methylcarbamate] sulfide;

N-[2-O-(N-methylcarbamoyl)oximino-1,3,5-trithiane] N-[2-(2-oxathiolanyl)phenyl N-methylcarbamate] sulfide;

N-[2-O-(N-methylcarbamoyl)oximino-1,4-dithiane] N-[2-propynyloxy phenylN-methylcarbamate] sulfide;

N-[5-Methyl-4-O-(N-methylcarbamoyl)oximino-oxathiolane]N-[4-phenoxyphenyl N-methylcarbamate] sulfide:

N-[4,5,5-Trimethyl-2-O-[N-methylcarbamoyl)oximinothiazolidin-3-one]N-[2-propynyloxy phenyl N-methylcarbamate] sulfide; and

N-[3,5,5-Trimethyl-2-O-[N-methylcarbamoyl]oximinothiazolidin-4-one]N-[2-(2-dithiolanyl)pheny

N-methylcarbamate] sulfide,

U.S. Pat. No. 4,315,928, incorporated herein by reference, discloses andclaims N-aminosulfenyl carbamate compounds which are encompassed by theabove formula 1 and which may be used in the method of this invention,Such N-aminosulfenyl carbamate compounds can be prepared by the methodsdescribed in U.S. Pat. No. 4,315,928, and are available from UnionCarbide Agricultural Products Company, Inc., Research Triangle Park,N.C. Illustrative of the N-aminosulfenyl carbamate compounds of U.S.Pat. No. 4,315,928 which may be useful in the method of this inventioninclude the following:

S-methyl N-[N'-methyl-N'-(diisopropylaminosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl N-[N'-methyl-N'-(di-n-butylaminosulfenyl) carbamoyloxy]thioacetimidate;

2-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]imino-1,4-dithiane;

S-methylN-[N'-methyl-N'-(morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-ethyl-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-isopropyl-n'[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy)thioacetimidate;

S-(2-cyanoethyl)-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-(1-butyl)-N-[N'-methyl-N'-(4-morpholinosulfenyl)carboxyloxy]thioacetimidate;

S-phenyl-N-[N'-methy-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-(aminocarbonylmethylene)-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thiopropionimidate;

S-methyl-N-[N'-ethyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-isopropyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-phenyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-(3-chlorophenyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(4-methyl-1-piperazinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(3-tetrahydro-1,3-oxazinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N'[N'-methyl-N'-(4-thiomorpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(dimethylaminosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-N'-methyl-N'-(methylethylaminosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(methylphenylaminosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'(methylbenzylaminosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(ethylcyclohexylaminosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'-methyl-N'-(methoxymethylaminosulfenyl)carbamoyloxy]thioacetimidate;

O-ethyl-N-[N'-methyl'N'-(4-morpholinosulfenyl)carbamoyloxy]acetimidate;

2-Methyl-2-(methylthio)propionaldehydeO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

2-methyl-2-(methylsulfonyl)propionaldehydeO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

2-cyano-2-methylpropionaldehydeO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

5-methyl-4-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxyl]imino-1,3-oxathiolane;

2-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]imino-1,4-oxathiane;

2-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]imino-1,4-dithiane;

3,3-Dimethyl-2-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]imino-5-oxo-perhydro-1,4-thiazine;

5,5-Dimethyl-4-N-[N'-methyl'N'-(4-morpholinosulfenylcarbamoy)oxy]imino-1,3-dithiolane;

2-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]imino-3,5,5-trimethyl-1,3-thiazolidine-4-one;

S-Methyl-N-[N'-Methyl-N'-(3,3-Dimethyl-4-Morpholinosulfenyl)carbamoyloxy]thioacetimidate;

2-methyl-2-nitropropionaldehydeO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

N-methyl-N-(4-morpholinosulfenyl) 3-isopropylphenyl carbamate;

N-methyl-N-(4-morpholinosulfenyl) 3-sec-butylphenyl carbamate;

N-methyl-N-(4-morpholinosulfenyl) 2-isopropoxyphenyl carbamate;

N-methyl)-N-(4-morpholinosulfenyl) 4-dimethylamino-3,5-xylyl carbamate;

N-methyl-N-(4-morpholinosulfenyl) 4-dipropylamino-3,5-xylyl carbamate:

N-methyl-N-(4-morpholinosulfenyl) 4-methylthio-3,5-xylyl carbamate;

N-methyl-N-(4-morpholinosulfenyl) 4-methylthio-3tolyl carbamate;

N-methyl-N-4-morpholinosulfenyl) 2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-(diisopropylamibosulfenyl)2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-methyl-N-(dimethylaminosulfenyl)2,3-dihydro-2,2dimethyl-7-benzofuranyl carbamate;

N-methyl-N-(4-morpholinosulfenyl) 3-dimethylaminomethyleneaminophenylcarbamate;

N-methyl-N-(4-morpholinosulfenyl)2-dimethylcarbamoyl-3-methyl-5-pyrazolyl carbamate;

N-methyl-N-(4-morpholinosulfenyl) 3-isopropyl-5-methylphenyl carbamate;

N-methyl-N-(4-morpholinesulfenyl) 4-methoxy-3,5-xylyl carbamate;

N-methyl-N-(4-morpholinosulfenyl) 2-methoxy-4-methylphenyl carbamate;

N-methyl-N-(4-morpholinosulfenyl)2-chloro-4-methylphenyl carbamate;

N-methyl-N-(di-n-butylaminosulfenyl) 3-sec-amylphenyl carbamate:

N-methyl-N-(4-morpholinosulfenyl) 5,6-dimethyl5,6,7,8-tetrahydro1-naphthyl-carbamate;

2-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]-imino-1,3-dithiolane;

Propiophenone O-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime:

O-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]phenylglyoxylonitrileoxime;

1-chloro-1-(ethylthio)formaldehydeO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

S-[2-(N-methylcarbamoyloxy)ethyl]-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thiopropionimidate;

S-Methyl-1-dimethylcarbamoyl-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioformimidate:

O-Methyl-1-dimethylcarbamoyl-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]formimidate:

3,3-dimethyl-1-(methylthio)-2-butanoneO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime:

Alpha(methylcarbamoyloxy)acetophenoneO-[N-methyl-N-(4morpholinesulfenyl)carbamoyl]oxime;

Methyl 2-Methylpropenyl ketoneO-[N-methyl-N-(4morpholinesulfenyl)carbamoyl]oxime;

Alpha(methylsulfinyl)acetonphenoneO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

Exo-3-chloro-endo-6-cyano-2-norbornanoneO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

S-isopropyl-1-acetyl-N-[N'-methyl-N'(4-morpholinosulfenyl)carbamoyloxy]thioformimidate:

5,5-dimethyl-1,4-dithia-6-N-[N'-methyl-N'-(4-morpholinosulfenyl)carbamoyloxy]-iminocycloheptane;

2,4-dimethyl-1,3-dithiolane-2-carboxaldehydeO-[N-methyl-N-(4morpholinosulfenyl)carbamoyl)oxime;

Isopropyl 5-(methylthio)-2-thienyl ketone O-[N-methylN-(4-morpholinosulfenyl)carbamoyl]oxime;

2,2-dimethyl-3-hydroxypropionaldehydeO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

2,2-dimethyl-3-(methylsulfonyloxy)propionaldehydeO-[N-methyl-N-(4-morpholinosulfenyl)carbamoyl]oxime;

3,3-dimethyl-4-N-[N-methyl-N-(4-morpholinosulfenyl)carbamolyoxy]imino-tetrahydrothiophene;

S-methyl-N-[N'-methoxymethyl-N'-(4-morpholinosulfenyl)carbamoyloxy)thioacetimidate;

S-methylN-[N'-allyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-(2-chloroethyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methyl-N-[N'cyanomethyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-benzyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'methoxy-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-(2-furylmethyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-(1-acetyl-3-piperidylmethyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-(3-tetrahydrothiophenylmethyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-cyclohexyl-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-(4-nitrophenyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;

S-methylN-[N'-(4-methoxyphenyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate;and

S-methylN-[N'-(2-chloro-4-methylphenyl)-N'-(4-morpholinosulfenyl)carbamoyloxy]thioacetimidate.

U.S. Pat. No. 4,072,751, incorporated herein by reference, discloses andclaims N-substituted bis-carbamoyl sulfide compounds which areencompassed by the above formula 1 and which may be used in the methodof this invention, Such N-substituted bis-carbamoyl sulfide compoundscan be prepared by the methods described in U.S. Pat. No. 4,072,751, andare available from Union Carbide Agricultural Products Company, Inc.,Research Triangle Park, N.C. Illustrative of the N-substitutedbis-carbamoyl sulfide compounds of U.S. Pat. No. 4,072,751 which may beuseful in the method of this invention include the following:

1-Methylsulfinyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyloxy]acetimidate;

S-Methyl-N-[N'[N"-(1-methysulfinylethylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxy]thioacetimidate;

S-Methyl-N-[N'-[N"-(1-methylsulfonyl-thylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'methylcarbamoyloxy]thioacetimidate;

1-Methyl-N-[(N'-[N"-(1-methylsulfinyl-thylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxy]-sulfinylacetimidate;

1-Methylsulfonyl-N-[N'-N"-(1-methylsulfonylthylidiniminooxycarbonyl)N"-methylaminosulfenyl]N'metylcarbamoyloxy]acetimidate;

1-Isopropylsulfinyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyloxy]acetimidate;

1-Pentylsulfonyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonyaminosulfenyl)carbamoyloxy]acetimidate;

S-Isopropyl-N-[N'-[N"-(1-methylsulfinylethylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxy[thioacetimidate;

S-Isopropyl-N-[N'-[N"-(1-isopropylsulfinylethylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxy]thioacetimidate;

S-Isopropyl-N-[N'-[N"-(1-isopropylsulfonylethylidiniminooxycarbonyl)-N'-methylaminosulfenyl]-N'-methylcarbamoyloxy]thioacetimidate;

1-Isopropylsulfonyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyloxy]acetimidate; and

1-Butylsulfinyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyloxy]acetimidate.

U.S. Pat. Nos. 4,486,477 and 4,400,389, incorporated herein byreference, disclose and claim symmetrical bis-sulfenylated bis-carbamatecompounds which are encompassed by the above formula 1 and which may beused in the method of this invention, Such symmetrical bis-sulfenylatedbis-carbamate compounds can be prepared by the methods described in U.S.Pat. Nos. 4,486,447 and 4,400,389, and are available from Union CarbideAgricultural Products Company, Inc., Research Triangle Park, N.C.Illustrative of the symmetrical bis-sulfenylated bis-carbamate compoundsof U.S. Pat. Nos. 4,486,447 and 4,400,389 which may be useful in themethod of this invention include the following:

1,2-Bis-[[N-methyl-N-[N'-(1-ethylthioethylideneiminooxycarbonylN-methylaminosulfenyl]carbamoyloxy]ethane;

2,2'-Bis-[[N-methyl-N-[N'-(1-isopropylthioethylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diethylether;

1,6-Bis-[[N-methyl-N-[N'-(1-butylthioethylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]hexane;

4,4'-Bis-[[N-methyl-N-[N'(2-methyl-2-methylthiopropylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]biphenyl;

4,4'-Bis-[[N-methyl-N-[N'-(2-methyl-2-methylsulfonylpropylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diphenylsulfide;

1,2-Bis-[[N-methyl-N-[N'-(2-methylsulfonylpropylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]benzene;

1,2-Bis-[[N-methyl-N-[N'-(1,3-dithiane-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]-carbamoyloxy]]

1,2-Bis-[[N-methyl-N-[N'-(1,3-dithiolane-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

2,2'-Bis-[[N-methyl-N-[N'-(thiophane-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]-carbamoyloxy]]diethyether;

1,6-Bis[[N-methyl-N-[N'(thiophane-3-ylideneimioxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]hexane;

1,4-Bis-[[N-methyl-N-[N'-(3,3-dimethyl-1,4-dioxane-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]2-butene;

1,2-Bis-[[N-methyl-N-[N'-(4-methyl-1,4-thiazine-3-one-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]ethane;

1,2-Bis-[[N-methyl-N-[N'-(4-methyl-1,4-oxazine-3-one-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

1,2-Bis-[[N-methyl-N-[N'-(3,3-dimethyl-1,4-thiazine-5-one-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

1,2-Bis-[[N-methyl-N-[N'-(1,3,5-trithiane-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

1,2-Bis[[N-methyl-N-[N'-(1,3,5-oxadithiane-4-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane:

2,2'-Bis-[[Bis-[[N-methyl-N-[N-40-(2-methylimino,5,5-dimethyl-4-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]diethyl]]ether;

2,2'-Bis-[[N-methyl-N-[N'-(1,4-oxathiane-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]diethylsulfide;

2,2'-Bis-[[N-methyl-N-[N'-(4,5,5-trimethyl-thiazolidin-3-one-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diethylsulfide;

1,2-Bis-[[N-methyl-N-[N'-(3,5,5-trimethyl-thiazolidin-4-one-2-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

2-Bis-[[N-butyl-N-[N'-(1-methylthioethylideneiminooxycarbonyl)-N'-butylaminosulfenyl]carbamoyloxy]]ethane;

1,2-Bis[[N-methyl-N-[N'-(3,3-dimethyl-1-methylthio-2-butylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]ethane;

2,2-Diphenyl-4,4'-bis[[N-butyl-N-[N'-(1,4-dithiane-4-oxide-2-ylideneiminooxycarbonyl)-N'-butylaminosulfenyl]carbamoyloxy]]propane;

2,2'-Bis-[[N-methyl-N-[N'-(5,5-dimethyl-1,3-dithiolane-4-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diethylsulfone;

2,2'-Bis-[[N-methyl-N-[N'-(5-methyl-1,3-oxathiolane-4-ylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diethylether;

1,2-Bis-[[N-methyl-N-[N'-(3,5-diisopropylphenyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

6-Bis[[N-methyl-N-[N'-(2-isopropoxyphenyloxycarbonyl-N'-methylaminosulfenyl]carbamoyloxy]]hexane;

2,2'-Bis[[N-methyl-N-[N'-(3,5-dimethyl-4-methylthiophenyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]diethylether;

1,2-Bis-[[N-methyl-N-[N'-(1-naphthyloxycarbonyl)-N'methylaminosulfenyl]carbamoyloxy]]ethane;

1,2-Bis-[[N-methyl-N-[N'-4-(2,2-dimethylbenzodioxanyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

2,2'-Bis-[[N-methyl-N-[N'-(3,5-dimethyl-4-dimethylaminophenyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diethylether;

1,2-Bis-[[N-methyl-N-[N'-(3-isopropyl-4-dimethylaminomethyleneiminophenyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane,di-hydrochloride;

4,4'-Bis-[[N-methyl-N-[N'-(2-ethylthiomethylphenyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diphenylether;

4,4'-Bis-[[N-methyl-N-[N'-2-chlorophenyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]diphenylsulfide;

1,4-Bis-[[N-methyl-N-[N'-7-(2,3-dihydro-2-methylbenzofuranoxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]-2-butyne;

1,4-Bis-[[N-methyl-N-(2-propynyloxyphenyloxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]-2-butene;

1,2-Bis-[[N-methyl-N-[N'-(1-(2-cyanoethylthio)ethylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane;

1,2-Bis-[[N-methyl-N-[N'-(2-cyano-2-methylpropylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]benzene;

1,2-Bis-[[N-methyl-N-[N'-(2-methyl-2-nitropropylideneminosulfenyl]carbamoyloxy]ethane;

1,2-Bis-[[N-methyl-N-[N'-(3,3-dimethyl-1-methylsulfinyl2-butylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]ethane;and

1,2-Bis-[[N-methyl-N-[N'-(1-dimethylaminocarbonyl-1-methylthiomethylideneiminooxycarbonyl)-N'-methylaminosulfenyl]carbamoyloxy]]ethane.

U.S. Pat. Nos. 4,327,110 and 4,413,007, incorporated hezein byreference, disclose and claim symmetrical N-substitutedbis-carbamoyloximino disulfide compounds which are encompassed by theabove formula 1 and which may be used in the method of this invention,Such symmetrical N-substituted bis-carbamoyloximino disulfide compoundscan be prepared by the methods described in U.S. Pat. Nos. 4,327,110 and4,413,007, and are available from Union Carbide Agricultural ProductsCompany, Inc., Research Triangle Park, N.C. Illustrative of thesymmetrical N-substituted bis-carbamoyloximino disulfide compounds ofU.S. Pat. Nos, 4,327,110 and 4,413,007 which may be useful in the methodof this invention include the following:

N-N'-bis-[1-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis-[1-IsopropylthioacetaldehydeO-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis-[1-(2-Cyanoethylthio)acetaldehydeO-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis[5-Methyl-4-(O-(N-methylcarbamoyl)oximino)-1,3-oxathiolane]disulfide;

N,N'-bis-[2-(O-(N-Methylcarbamoyl)-1,4-dithiane]disulfide;

N,N'-bis-[4-(O-(N-Methylcarbamoyl)oximino)-1,3-dithiolane]disulfide;

N,N'-bis-[5,5-Dimethyl-4-(O-(N-methylcarbamoyl)oximino)-1,3-dithiolane]disulfide;

N,N'-bis-[3,5,5-Trimethyl-2-(O-(N-methylcarbamoyl)oximino)-thiazolidin-4-one]disulfide;

N,N'-bis-[4,5,5-Trimethyl-2-(O-(N-methylcarbamoyl)oximino)-thiazolidin-3-one]disulfide;

N,N'-bis-[2-(O-(N-Methylcarbamoyl)oximino)-1,3-dithiolane]disulfide;

N,N'-bis-[2-Cyano-2-methylpropionaldehydeO-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis-[1-Methylthio-N",N"-dimethylcarbamoylformaldehydeO-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis-[4-Methyl-2-(O-(N-methylcarbamoyl)oximino)tetrahydro-1,4-thiazin-3-one]disulfide;

N,N'-bis-[3,3-Dimethyl-1-methylthiobutanone-2O-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis-[3-Methylsulfonylbutanone-2O-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis-[2-Methylsulfonyl-2-methylpropionaldehyde-O-(N-methylcarbamoyl)oxime]disulfide:

N,N'-bis-[1-MethylthiopyruvaldehydeO-(N-methyl-carbamoyl)oxime)disulfide;

N,N'-bis-[3,3-Dimethyl-1-methylsulfonylbutanone-2-O-(N-methylcarbamoyl)oxime]disulfide:

N,N'-bis-1-[N-(Dimethylaminomethylene)carbamoyl-1-methylthioformaldehydeO-(N-methylcarbamoyl)oxime]disulfide:

N,N'-bis-[1-Methylthio-1-ethoxycarbonylformaldehyde-O-(N-methylcarbamoyl)oxime]disulfide;

N,N'-bis-[1,3,5-Oxadithiane-4 O-(N-methylcarbamoyloximino)]disulfide;

N,N'-bis-[(O-(N-Methylcarbamoyl)oximino-1,4-oxathiane]disulfide;

N,N'-bis-[1-Cyano-2,2-dimethylpropionaldehydeO-(N-methylcarbamoyl)oxime]disulfideN,N'-bis-[4-Methyl-2-(O-(N-methylcarbamoyl)oximino)tetrahydro-1,4-thiazin-5-one]disulfide;

N,N'-bis-[1-Methylthloacetaldehyde O-(N-butylcarbamoyl)oxlme]disulfide;and

N,N'-bis-[1,3,5-Trithiane-2 O-(N-methylcarbamoyl)oximino]disulfide,

Other sulfur-containing compounds disclosed in the art and encompassedwithin the formula 1 may also be used in the method of this invention,Such sulfenylated compounds including the preparation thereof aredescribed in the following U.S. Pat. Nos.: 4,208 409; 4,444,786;4,413,005: 4,298,617; 4,315,027; 4,410,518; 4,006,231; 4,342,778; 13,847,951; 4,103,024; 4,113,876; 4,148,910; 4,008,328; 4,511,578;4,424,213; 4,225,615; 4,268,520: and 4,160,034.

Illustrative of these other sulfur-containing compounds which may beuseful in the method of this invention include the following:

7-[N-methyl-N-[N'-methyl-N'[butoxycarbonyl]aminosulfenyl]carbamoyloxy]-2,3-dihydro-2,2-dimethylbenzofuran(furathiocarb);

MethylN-methyl-N-[N'-tert-butyl-N'-[5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl]aminosulfenyl]carbamoyloxy]ethanimidothioate;

MethylN-[[[[[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)lsopropylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[(5,5dimethyl-2-thioxo-1,3,2dioxphosphorian-2-yl)tert-butylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[isopropyl(5,5-diethyl-2-thioxo-1,3,2-phosphorinan-2-yl)amino]thio]amino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[ethyl(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]amino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[isopropyl(2-thioxo-1,3,2-phospholan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[isopropyl(2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[isopropyl(4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[cyclohexyl(5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[cyclohexyl(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[methyl(2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate;

S-MethylN-[(N-Methyl-N-(N-methyl-N-ethoxycarbonylmethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N-n-butyl-N-methoxycarbonylmethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N-phenyl-N-ethoxycarbonylmethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-methyl-N-(N-phenyl-N-ethoxycarbonylmethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N-benzoyl-N-ethoxycarbonylmethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N-n-propyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N-ethoxycarbonyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N,N-bis(ethoxycarbonylmethyl)aminosulfenyl)carbamoyl)oxy]thioacetamidate;

S-MethylN-[(N-Methyl-N-(N,N-bis(ethoxycarbonylethyl)aminosulfenyl)carbamoyl)oxy]thioacetamidate;

2,3-Dihydro-2,2-dimethylbenzofuran-7-ylN-[N,N-bis(ethoxycarbonylmethyl)aminosulfenyl]-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuran-7-ylN-(N-methyl-N-ethoxycarbonylmethylaminosulfenyl)-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuran-7-ylN-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuran-7-ylN-(N-n-butyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuran-7-ylN-(N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuran-7-ylN-(N-n-butyl-N-cyanoethylaminosulfenyl)-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuranyl-7N-[(N'-isopropoxycarbonyl)-N'-(methylaminosulfinyl)]-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuranyl-7N-[N'-(methoxycarbonyl)-N'-(methylaminosulfinyl)]-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuranyl-7N-[N'-(methoxycarbonyl)-N'-(methylaminosulfinyl)]-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuranyl-7N[N'-(n-propoxycarbonyl)-N'-(methylaminosulfinyl)]-N-methylcarbamate;

2,3-Dihydro-2,2-dimethylbenzofuranyl-7N-[N'-(n-heptoxycarbonyl)-N'-(methylaminosulfinyl)]-N-methylcarbamate;

N,N'-sulfinyldi-[S-methyl N"-(methylcarbamoyloxy)thioacetimidate];

N'-sulfinyldi-[2-methyl-2-(methylthio)propionaldhydeO-methylcarbamoyloxime];

N,N'-sulfinyldi-[S-methylN",N"-dimethyl-N"'-methylcarbamoyloxy-1-thio-oximidate];

N,N'-sulfinyldi-[3,3-dimethyl-1-(methylthio)butanoneO-methylcarbamoyloxime];

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl[[(diethoxyphosphinothioyl)methylamino]sulfinyl]methylcarbamate;

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl[[(diethoxyphosphinothioyl)hexylamino]sulfinyl]methylcarbamate;

MethylN-[[[[[(dimethoxyphosphinothioyl)methylamino]sulfinyl]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[(diethoxyphosphinothioyl)ethylamino]sulfinyl]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[(diethoxyphosphinothioyl)hexylamino]sulfinyl]methylamino]carbonyl]oxy]ethanimidothioate;

MethylN-[[[[[(diethoxyphinothioyl)isopropylamino]sulfinyl]methylamino]carbonyl]oxy]ethanimidothioate;

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl[[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)methylamino]sulfinyl]methylcarbamate;

Methyl N-[[[[[(5,5-dimethyl-2-thioxo1,3,2-dioxaphosphorinan-2-yl)(methyl)amino]sulfinyl]methylamino]carbonyl]oxy]ethanimidothioate;

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl(dimethylaminosulfenyl)(methyl)carbamate;

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl(methyl)(morpholinosulfenyl)carbamate;

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl(methyl)(piperidinosulfenyl)carbamate;

N-methyl-N-methylthio-2,3-dihydro-7-benzofuranyl carbamate;

N-methyl-N-methylthio-2,3-dihydro-7-benzofuranyl carbamate;

N-methyl-N-methylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-methyl-N-ethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-methyl-N-propylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-isobutylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-ethyl-N-butylthio-2,3-dihydro-2,2-diethyl-7-benzofuranyl carbamate;

N-methyl-N-hexylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-methyl-N-decylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-methyl-N-dodecylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-butyl-N-vinylthio-2,3-dihydro-2-methyl-2-ethyl-7-benzofuranylcarbamate;

N-butyl-N-propenylthio-2,3-dihydro-2,2-dipropyl-7-benzofuranylcarbamate;

N-propyl-N-2-butenylthio-2,3-dihydro-2,2-dibutyl-7-benzofuranylcarbamate;

N-methyl-N-3-heptenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-2-bromoethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-methyl-N-2,2-dichloroethylthio-2,3-dihydro-7-benzofuranyl carbamate;

N-methyl-N-2,2,2-trifluoroethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-2,2,2-trichloroethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-1,2,2-tribromoethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-1,2-difluoroethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-2-bromoethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-1,2,2,2-tetrachloroethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-1,1,2,2-tetrachloroethylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-3,6-dibromohexylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-trichlorovinylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-tribromovinylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-alpha -naphthylthio-2,3-dihydro-2,2-dimethylbenzofuranylcarbamate;

N-methyl-N-phenylthio-2,3-dihydro-7-benzofuranyl carbamate;

N-methyl-N-phenylthio-2,3-dihydro-2-methyl-7-benzofuranyl carbamate;

N-methyl-N-phenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranyl carbamate;

N-methyl-N-4-chlorophenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-4-fluorophenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-3,5-dichlorophenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-2,4-dichlorophenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-3-chloro-5-methylphenylthio-2,3-dihydro-2-methyl-7-benzofuranylcarbamate;

N-ethyl-N-2-bromophenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-4-methylphenylthio-2,3-dihyro-7-benzofuranyl carbamate;

N-4-chlorophenylthio-2,3-dihydro-2-methyl-7-benzofuranyl carbamate;

N-methyl-N-4-ethylthiophenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-N-o-nitrophenylthio-2,3-dihydro-2,2-7-benzofuranyl carbamate;

N-methyl-N-o-nitrophenyl-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-methyl-p-nitrophenylthio-2,3-dihydro-2,2-dimethyl-7-benzofuranylcarbamate;

N-Methyl-N-(2-toluenesulphonic acidmethylamide-N'-sulphenyl)-2,2-dimethyl-2,3-dihydrobenzofuranyl-(7)-carbamate;

(3-Trifluoromethyl-benzenesulfonicacid-N'-methylamido-N'-sulfenyl)-N-methyl-carbamic acid ester of2-(1',3'-dioxolan(2')yl)-phenol;

(2-Nitro-benzenesulfonicacid-N'-methylamido-N'-sulfenyl)-N-methyl-carbamic acid ester of2,2-dimethyl-2,3-dihydro-7-hydroxybenzofuran;

N-methyl-N-(3-trifluoromethylphenylsulfenyl)-1-methylthioacetaldoxime-carbamate;

1,3-thiolane-2-oximino-carbamate;

N-methyl-N-(3-trifluoromethylpheny]sulfenyl);

N-methyl-N-(3-trifluoromethylphenylsulfenyl)-2-methyl-2-methylthiopropionaldoxime-carbamate;

N-methyl-N-(3-trifluoromethylphenylsulfenyl)-1-methylthioglyoxylic aciddimethylamide oximecarbamate; and

Isobutyryl-N-methylamidosulfenyl-N'-methyl-[2,2-dimethyl-2,3-dihydrobenzofuranyl(7)]carbamate.

It is appreciated that the particular sulfur-containing compounds listedhereinabove are illustrative of sulfur-containing compounds which may beused in the method of this invention. The method of this invention isnot to be construed as being limited only to the use of thesesulfur-containing compounds; but rather, the method of this inventionincludes those sulfur-containing compounds encompassed within formula 1hereinabove.

The sulfur-containing compounds of formula 1 are effective in theprotection of developing plants against attack by plant parasiticnematodes. These sulfur-containing compounds are particularly useful onnematode pests of agricultural crops such as soybeans, corn, cotton,wheat, rice, vegetables, bearing and non-bearing fruit, and ornamentals.The sulfur-containing compounds are effective against a wide range ofnematode pests including species of Meloidogyne, Heterodera, Globodera,Rotylenchulus, Pratylenchus, Aphelenchoides, Helicotylenchus,Hoplolaimus, Paratrichodorus and Tylenchorhynchus. Because of systemicactivity possessed by many of the sulfur-containing compounds of formula1 these compounds are effective not only against a wide variety of soilnematodes but also against stem, bulb and foliar nematodes and otherpests by practicing the method of this invention.

The residual activity in agricultural soil is relatively short forcertain of the sulfur-containing compounds of formula 1, e,g..thiodicarb. and if applied to the soil at the time of or prior toplanting, these compounds may not remain active for a sufficient periodof time to provide optimum protection of developing plants from attackby plant parasitic nematodes. However, because of the nematicidalproperties of these sulfur-containing compounds and because many ofthese compounds exhibit no or minimal phytotoxicity to most plantspecies and are systemic, application of these compounds to seeds, seedpieces and bare root systems allows for protection of plants, especiallyseedlings or young plants, from attack by nematodes. The most criticalphenological stage of many agricultural crop species is during seedlingestablishment. Early season protection against stress factors includingparasitism by nematodes is important in the overall yield and qualitycapacity of the plant. This invention provides an effective method forutilizing such short residual systemic compounds as nematicides for cropprotection.

The sulfur-containing compounds of formula 1 may be applied to seed,seed pieces, or roots of plants by conventional methods known in theart. Such methods include, but are not limited to, seed coating ordusting, root or seed piece dips, sprays, or coatings.

Formulated compositions containing a sulfur-containing compound as theactive ingredient will usually comprise a carrier and/or a diluenteither liquid or solid. Suitable liquid carriers include water,petroleum distillates or other liquid carriers with or withoutsurfactants. Liquid concentrates may be prepared by dissolving one ofthe sulfur-containing compounds with a nonphytotoxic solvent such asacetone, Xylene, or nitrobenzene and dispersing the active ingredient inwater with the aid of suitable surface active emulsifying and dispersingagents. The choice of dispersing and emulsifying agent and the amountused is dictated by the ability of the agent to facilitate thedispersion of the active ingredient. For solid carriers such as wettablepowders or dusts. the active ingredient is dispersed in and on anappropriately divided carrier such as clay, talc, bentonite,diatomaceous earth, and the like.

Formulations useful in the conduct of the method of this invention canalso contain other optional ingredients such as stabilizers or otherbiologically active compounds, insofar as they do not impair or reducethe activity of the sulfur-containing compounds towards the nematodes.

Treatment of seed, seed pieces, or roots can be accomplished by coating,spraying, dipping, dusting, or otherwise covering the organ with theactive ingredient with or without carriers, diluents and the like. Bothformulated and technical materials containing the active ingredient maybe used in the method of this invention. Seed or seed piece treatmentsranging from 0.1 to 10.0 percent active ingredient by weight of seed orseed pieces are generally effective depending on the particularsulfur-containing compound, plant species, and degree of controlrequired. Dipping of roots or seed pieces into solutions consisting ofthe active ingredient plus appropriate carriers, diluents, surfaceactive agents, and emulsifying or dispersing agents is effective atrates ranging from 0.001 to 10.0 percent active ingredient. Dippingtimes ranging from a few seconds to several hours are effective. Ratesof application of active ingredient and exposure time are dependent uponthe plant species treated, the nematode pests to be controlled, and thedegree of control desired.

In the following examples, the formulations uutilized were diluted withwater to give a suspension containing the active ingredient at theconcentrations set forth in each example. Conventional means wereutilized to coat seeds with both formulation and technical materials.Seeds were coated with a formulation by rotating in a standard rotarycoating pan containing the specified formulation until dry. Thethiodicarb technical methomyl technical and other technical materialswere dissolved in an acetone/triton mixture to give a suspensioncontaining the specified technical material at the concentrations setforth in the examples. Seeds were coated with a technical material bystirring in the specified technical material/acetone/triton suspensionand evaporating the acetone with an air hose. Thiodicarb technical isavailable from Union Carbide Agricultural products Company. Inc.,Research Triangle park, N.C. and methomyl technical is available fromE.I. du Pont de Nemours & Co., Inc. Agricultural Chemicals Dept.,Wilmington, Del.

EXAMPLE 1

Soybean seeds treated with LARVIN® brand thiodicarb insecticide 375 F,commercially available from Union Carbide Agricultural Products Company,Inc. Research Triangle Park, N.C., were planted in 10 centimeter fiberpots containing natural field soil. The concentrations of thiodicarbemployed (milligrams per 10 grams of soybean seeds) are given in Table Ibelow. At the time of planting, the natural field soil was inoculatedwith Heterodera glycines eggs and juveniles collected from crushedcysts. The treated soybean seeds were germinated and the root systemstested for nematode control 13 days after planting. The results aregiven in Table I. The top weight of the seedlings was determined 13 daysafter planting, and these results are also given in Table I. Nematodecontrol was determined by root staining and observation in which theroots were stained by boiling in acid fuchsin-acetic acid following a 4minute NaOCl pre-treatment. The top weight and nematode control resultsin Table I are the average of 3 repetitions

                  TABLE I                                                         ______________________________________                                        Soybean Seed Treatment                                                        Thiodicarb  Soybean Plant                                                     Concentration                                                                             Top Weight   No. of H. Glycines                                   (mg/10 gm seed)                                                                           (gm)         Juveniles/Root System                                ______________________________________                                        Control (Untreated)                                                                       3.3          132                                                  30          3.4           21                                                  60          3.4           9                                                   ______________________________________                                    

The results from Table I illustrate a significant reduction of H.glycines juveniles in soybean root systems grown from thiodicarb treatedsoybean seeds in comparison with soybean root systems groWn fromuntreated soybean seeds without any negative effect on plant growth.

EXAMPLE 2

Cotton seeds treated with LARVIN® brand thiodicarb insecticide 75 WP,commercially available from Union Carbide Agricultural Products Company.Inc., Research Triangle Park, N.C., plus Soilserve seed sticker wereplanted in 10 centimeter fiber pots containing artificial soil (peatmossand sand). The concentrations of thiodicarb employed (milligrams per 10grams of cotton seeds) are given in Table II below. At the time ofplanting, the artificial soil was inoculated with Meloidogyne incognitaeggs collected by NaOCl extraction in a water suspension. The treatedcotton seeds were germinated and the root systems observed for galling30 days after planting. The results are given in Table II. Nematodecontrol was determined by root gall ratings based on observation inwhich the rating scale used was as follows:

Rating scale of 1-5 wherein 1 indicates heavy galling and 5 indicates nogalling. The gall rating results in TabIe II are the average of 3repetitions.

                  TABLE II                                                        ______________________________________                                        Cotton Seed Treatment                                                         Thiodicarb                                                                    Concentration     Gall                                                        (mg/10 gm seed)   Rating                                                      ______________________________________                                        Control (Untreated)                                                                             1.0                                                          50               3.0                                                         100               3.3                                                         200               4.3                                                         400               4.7                                                         ______________________________________                                    

The results from Table II illustrate significantly less galling from M.incognita in cotton root systems grown from thiodicarb treated cottonseeds in comparison with cotton root systems grown from untreated cottonseeds.

EXAMPLE 3

Tomato seedlings (4-6 centimeters in height) were removed fromgermination flats and their root systems were washed and immersed ineither LARVIN® brand thiodicarb insecticide 375 F formulated to give 1percent thiodicarb, commercially available from Union CarbideAgricultural Products Company. Inc., Research Triangle park, N.C.,LANNATE® brand methomyl insecticide 225 formulated to give 1 percentmethomyl commercially available from E. I. du Pont de Nemours & Co.,Inc., Agricultural Chemical Dept., Wilmington. Del., thiodicarbtechnical or methomyl technical. The immersion period (exposure time)for each tomato seedling is given in Table III below. Following theimmersion period, the tomato seedlings were planted in 10 centimeterfiber pots containing sterilized (fumigated) field soil. At the time ofplanting the treated tomato seedlings, the sterilized field soil wasinoculated with Meloidogyne incognita eggs collected by NaOCl extractionin a water suspension. The tomato root systems were observed for gallingand egg masses 33 days after bare root dip treatment. The results aregiven in Table III. Nematode control was determined by root gall and eggmass ratings based on observation in which the rating scale used was asfollows:

Rating scale of 1-5 wherein 1 indicates heavy galling (numerous eggmasses) and 5 indicates no galling (egg masses absent). The root galland egg mass ratings and the top weight results in Table III are theaverage of 3 repetitions.

                  TABLE III                                                       ______________________________________                                        Tomato Seedling Bare Root Dip Treatment                                                      Exposure           Egg                                                        Time       Gall    Mass                                        Formulation    (min.)     Rating  Rating                                      ______________________________________                                        Control (water)                                                                              30         1.0     1.0                                         Control (Acetone)                                                                            30         1.0     1.0                                         LARVIN 375 F   1          3.0     5.0                                                        5          3.3     5.0                                                        15         3.0     4.6                                                        30         3.0     5.0                                         Thiodicarb Technical                                                                         30         3.0     5.0                                         LANNATE 225    1          --      --                                                         5          --      --                                                         15         --      --                                                         30         --      --                                          Methomyl Technical                                                                           30         --      --                                          ______________________________________                                    

The results from Table III illustrate significantly less galling and eggmasses from M. incognita in tomato root systems treated with thiodicarb(bare root dip treatment) in comparison with untreated tomato rootsystems (no bare root dip treatment). The tomato seedlings in which theroot systems were treated with LANNATE® brand methomyl insecticide 225and methomyl technical exhibited marked phytotoxicity and were all deadwithin 48 hours after treatment.

EXAMPLE 4

Cucumber seeds treated with the various compounds identified in Table IVbelow were planted in 10 centimeter fiber pots containing artificialsoil (peatmoss and sand). Each compound was employed as a technicalmaterial at a concentration of 500 milligrams per 10 grams of cucumberseeds. At the time of planting, the artificial soil was inoculated withMeloidocvne incognito eggs collected by NaOCl extraction in a watersuspension. The treated cucumber seeds were germinated and the rootsystems observed for galling 40 days after planting, The results aregiven in Table IV. Nematode control was determined by root gall ratingsbased on observation in which the rating scale used was as follows:

Rating scale of 1-5 wherein 1 indicates heavy galling and 5 indicates nogalling. The gall rating results in Table IV are the average of 3repetitions.

                                      TABLE IV                                    __________________________________________________________________________    Cucumber Seed Treatment                                                                                            Gall                                     Compound Structure                   Rating                                   __________________________________________________________________________    (i)                                                                              Control (Untreated)               1.0                                      (ii)                                                                              ##STR16##                        3.3                                      (iii)                                                                             ##STR17##                        4.0                                      (iv)                                                                              ##STR18##                        2.7                                      (v)                                                                               ##STR19##                        3.0                                      (vi)                                                                              ##STR20##                        2.7                                      (vii)                                                                             ##STR21##                        4.7                                      (viii)                                                                            ##STR22##                        2.3                                      __________________________________________________________________________

Compound (ii) is thiodicarb and is commercially available from UnionCarbide Agricultural Products Company, Inc., Research Triangle park,N.C. Compound (iii) was prepared in a manner similar to the proceduredescribed in U.S. Pat. No. 4,327,110. Compound (iv) was prepared in amanner similar to the procedure described in U.S. Pat. No. 4,341,795.Compounds (v) and (vii) were prepared in a manner similar to theprocedure described in U.S. Pat. No. 4,551,472. Compound (vi) isavailable from The Upjohn Company, Kalamazoo, Mich. Compound (viii) ismethomyl and is commercially available from E. I. du pont de Nemours &Co., Inc., Agricultural Chemical Dept., Wilmington, Del.

The results from Table IV illustrate significantly less galling from M.incognita in cucumber root systems grown from the treated cucumber seedsin comparison with cucumber root systems grown from untreated cucumberseeds. Phytotoxicity was observed in cucumber plants which had been seedtreated with compound (viii) i.e., methomyl.

EXAMPLE 5

Tomato seedlings (4-6 centimeters in height) were removed fromgermination flats and their root systems were washed and immersed ineither LARVIN® brand thiodicarb insecticide 375 F formulated to give 1percent thiodicarb. or LARVIN® brand thiodicarb insecticide 75 WPformulated to give 1 percent thiodicarb both commercially available fromUnion Carbide Agricultural products Company Inc., Research TrianglePark, N.C. The immersion period (exposure time) for each tomato seedlingis given in TabIe V below. Following the immersion period. the tomatoseedlings were planted in 10 centimeter fiber pots containing sterilized(fumigated) field soil. At the time of planting the treated tomatoseedlings, the sterilized field soil was inoculated with Meloidogyneincognita eggs collected by NaOCl extraction in a water suspension. Thetomato seedling foliage was inoculated with the larvae of SouthernArmyworm (Spodoptera eridania, (Cram.)) 18 days after bare root diptreatment. The tomato root systems were tested for nematode control 18days after bare root dip treatment. The results are given in Table V.The percent mortality of Southern Armyworm (SAW) was determined 19 daysafter bare root dip treatment (24 hour feeding period), and theseresults are also given in Table V. Nematode control was determined byroot staining and observation in which the roots were stained by boilingin acid fuchsin-acetic acid following a 4 minute NaOCl pre-treatment.The percent mortality Southern Armyworm was determined by counting thenumber of dead larvae. Larvae which were unable to move the length ofthe body, even upon stimulation by prodding were considered dead. Thenematode control and percent mortality Southern Armyworm results inTable V are the average of 3 repetitions.

                  TABLE V                                                         ______________________________________                                        Tomato Seedling Bare Root Dip Treatment                                                               No. of M.                                                                     incognita   SAW                                                    Exposure   Juveniles/  Percent                                   Formulation  Time (hr)  0.5 gm Root Mortality                                 ______________________________________                                        Control (Untreated)                                                                        1          172          0                                                     24         173          0                                        LARVIN 75 WP 1          3           100                                                    24         4           100                                       LARVIN 375 F 1          4           100                                                    24         2           100                                       ______________________________________                                    

The results from Table V illustrate a significant reduction of M.incognita juveniles in tomato root systems treated with thiodicarb (bareroot dip treatment) in comparison with untreated tomato root systems nobare root dip treatment). The Southern Armyworm foliage feed testevidenced the translocation (systemic activity) of thiodicarb to thetomato seedling foliage.

EXAMPLE 6

Corn seeds treated with LARVIN® brand thiodicarb insecticide 3.6 F andLARVIN® brand thiodicarb insecticide 500 F plus graphite, bothcommercially available from Union Carbide Agricultural products Company.Inc., Research Triangle park N.C., were planted in 10 centimeter fiberpots containing natural field soil. The concentrations of thiodicarbemployed (milligrams per 10 grams of corn seeds) are given in Table VIbelow. At the time of planting. the natural field soil was inoculatedwith Meloidogyne incognita eggs collected by NaOCl extraction in a watersuspension. The treated corn seeds were germinated and the root systemstested for nematode control 8 days after planting. The results are givenin Table VI. Nematode control was determined by root staining andobservation in which the roots were stained by boiling in acidfuchsin-acetic acid following a 4 minute NaOCl pre-treatment. Thenematode control results in Table VI are the average of 3 repetitions.

                  TABLE VI                                                        ______________________________________                                        Corn Seed Treatment                                                                       Thiodicarb    No. of M.                                                       Concentration incognita                                           Formulation (mg/10 gm seed)                                                                             Juveniles/gm Root                                   ______________________________________                                        Control (Untreated)                                                                       0             18                                                  LARVIN 3.6 F                                                                              50            2                                                               163           1                                                               241           1                                                   LARVIN 500 F +                                                                            90            1                                                   Graphite    129           0                                                   ______________________________________                                    

The results from Table VI illustrate a significant reduction of M.incognita juveniles in corn root systems grown from thiodicarb treatedcorn seeds in comparison with corn root systems grown from untreatedcorn seeds.

EXAMPLE 7

Cotton seeds treated with LARVIN® brand thiodicarb insecticide 80 DF,commercially available from Union Carbide Agricultural products Company,Inc., Research Triangle park, N.C., were planted in 10 centimeter fiberpots containing artificial soil (peat moss and sand). The concentrationsof thiodicarb employed in weight (ounces) per hundred pounds (cwt) ofcotton seeds are given in Table VII below. At the time of planting theartificial soil was infested with Helicotylenchus dihystera. Hoplolaimusgaleatus, Paratrichodorus christiei, Pratylenchus brachyurus, andTylenchorhynchus claytoni nematode species. The cotton seeds weregerminated and the root systems tested for nematode control 8 weeksafter planting. Nematode populations in the soil were also determinedbased on a 100 cubic centimeter sample of the soil, The results aregiven in Table VII. The procedures used for determining nematodepopulations in root systems and nematode populations in soil aredescribed in Rodriguez-Kabana. R. et al.. 1981. Nematropica 1:175-186.The results in TabIe VII are the average of 8 repetitions.

                                      TABLE VII                                   __________________________________________________________________________    Cotton Seed Treatment                                                         Thiodicarb                  No. of Nematodes-                                 Concen-                                                                             No. of Nematodes - Root System                                                                      Soil System                                       tration                                                                             P.    T.    H.   H.   P.    T.                                          (oz/cwt)                                                                            brachyurus                                                                          claytoni                                                                            dihystera                                                                          galeatus                                                                           christiei                                                                           claytoni                                    __________________________________________________________________________    Control                                                                             107   109   941  56   364   129                                         (untreated)                                                                   6      19   40    335  15   236   28                                          8      8    37    273   7   144   47                                          __________________________________________________________________________

The results from Table VII illustrate a significant reduction of allnematode species in cotton root systems grown from thiodicarb treatedcotton seeds in comparison with cotton root systems grown from untreatedcotton seeds, and also a significant reduction of p. christiei and T.claytoni populations in soil systems having thiodicarb treated cottonseeds germinated therein in comparison with soil systems havinguntreated cotton seeds germinated therein.

EXAMPLE 8

Soybean seeds treated with LARVIN® brand thiodicarb insecticide 90 MC,commercially available from Union Carbide Agricultural products Company,Inc., Research Triangle park. N.C., and with one or both of thefungicides ORTHOCIDE® brand captan fungicide 30 DD commerciallyavailable from Chevron Chemical Company, Ortho Agricultural ChemicalsDivision, San Francisco, Calif., and VITAVAX® brand carboxin fungicide30 C commercially available from Uniroyal Chemical, Division of UniroyalInc., Middlebury, Conn., were planted in 10 centimeter fiber potscontaining natural field soil. The concentrations of thiodicarb, captanand carboxin employed in weight (ounces) per hundred pounds (cwt) ofsoybean seeds are given in Table VIII below. At the time of planting,the natural field soil was infested with Meloidogyne incognita,Paratrichodorus christiei, Heterodera glycines and Sapronhagus nematodespecies. Saprophagus is a group of free-living nematodes which are notplant parasitic, The soybean seeds were germinated and the root systemstested for nematode control 8 weeks after planting. The results aregiven in Table VIII. The procedure used for determining the nematodepopulations in the root systems is described in Rodriguez-Kabana, R. etal.. 1981. Nematropica 11:175-186. The results in Table VIII are theaverage of 8 repetitions.

                                      TABLE VIII                                  __________________________________________________________________________    Soybean Seed Treatment                                                        Thiodicarb                                                                          Captan                                                                             Carboxin                                                           Concen-                                                                             Concen-                                                                            Concen-                                                                            No. of Nematodes - Root System                                tration                                                                             tration                                                                            tration                                                                            M.   P.   H.                                                  (oz/cwt)                                                                            (oz/cwt)                                                                           (oz/cwt)                                                                           incognita                                                                          christiei                                                                          glycines                                                                           Saprophagus                                    __________________________________________________________________________    Control                                                                             --   --   730  22   5    128                                            (untreated)                                                                   16    3.3  0    263  12   3    128                                            16    3.3  3.3  256  2    0    102                                            24    3.3  0    110  1    1    52                                             24    3.3  3.3  131  2    0    83                                             32    3.3  0    219  2    0    59                                             32    3.3  3.3  102  1    0    74                                             __________________________________________________________________________

The results from TabIe VII illustrate a slgnificant reduction of allnematode species in soybean root systems grown from thiodicarb treatedsoybean seeds in comparison with soybean root systems grown fromuntreated soybean seeds.

EXAMPLE 9

Rye seeds (Secale cereale) treated with LARVIN® brand thiodicarbinsecticide 90 MC, commercially available from Union CarbideAgricultural products Company, Inc., Research Triangle park N.C., andwith on or both of the fungicides, ORTHOCIDE® brand captan fungicide 30DD commercially available from Chevron Chemical Company, OrthoAgricultural Chemicals Division, San Francisco, Calif., and VITAVAX®brand carboxin fungicide 30 C commercially available from UniroyalChemical, Division of Uniroyal, Inc., Middlebury, Conn., were planted in10 centimeter fiber pots containing natural field soil. Theconcentrations of thiodicarb, captan and carboxin employed in weight(ounces) per hundred pounds (cwt) of rye seeds are given in Table IXbelow. At the time of planting, the natural field soil was infested wirhParatrichodorus christiei and Saprophagus nematode species. Saprophagusis a group of free-living nematodes which are not plant parasitic. Therye seeds were germinated and the root systems tested for nematodecontrol 6 weeks after planting. The results are given in Table IX. Theprocedure used for determining the nematode populations in the rootsystems is described in Rodriguez-Kabana, R. et. al., 1981. Nematropica11:175-186. The results in Table IX are the average of 8 repetitions.

                  TABLE IX                                                        ______________________________________                                        Rye Seed Treatment                                                                      Captan   Carboxin  No. of Nematodes -                               Thiodicarb                                                                              Concen-  Concen-   Root System                                      Concentration                                                                           tration  tration   P.                                               (oz/cwt)  (oz/cwt) (oz/cwt)  christiei                                                                            Saprophagus                               ______________________________________                                        Control   --       --        39     21                                        (untreated)                                                                   16        3.3      0         16     12                                        16        3.3      3.3       25     10                                        24        3.3      0         16     16                                        24        3.3      3.3        5      6                                        32        3.3      0          7     15                                        32        3.3      3.3        7      6                                        ______________________________________                                    

The results from Table IX illustrate a significant reduction of allnematode species in rye root systems grown from thiodicarb treated ryeseeds in comparison with rye root systems grown from untreated ryeseeds.

EXAMpLE 10

Wheat seeds (Triticum aestivum) treated with LARVIN® brand thiodicarbinsecticide 90 MC, commercially available from Union CarbideAgricultural Products Company, Inc., Research Triangle Park, N.C., andwith one or both of the fungicides, ORTHOCIDE® brand captan fungicide 30DD commercially available from Chevron Chemical Company, OrthoAgricultural Chemicals Division, San Francisco, Calif., and VITAVAX®brand carboxin fungicide 30 C commercially available from UniroyalChemical, Division of Uniroyal. Inc., Middlebury, Conn., were planted in10 centimeter fiber pots containing natural field soil. Theconcentrations of thiodicarb, captan and carboxin employed in weight(ounces) per hundred pounds (cwt) of wheat seeds are given in Table Xbelow. At the time of planting, the natural field soil was infested withMeloidogyne incognita, Paratrichodorus christiei and Saprophagusnematode species. Saprophagus is a group of free-living nematodes whlchare not plant parasitic. The wheat seeds were germinated and the rootsystems tested for nematode control 6 weeks after planting. The resultsare given in Table X. The procedure used for determining the nematodepopulations in the root systems is described in Rodriguez-Kabana, R. etal., 1981. Nematropica 11:175-186. The results in Table X are theaverage of 8 repetitions.

                  TABLE X                                                         ______________________________________                                        Wheat Seed Control                                                            Thiodicarb                                                                            Captan   Carboxin  No. of Nematodes -                                 Concen- Concen-  Concen-   Root System                                        tration tration  tration   M.     P.      Sapro-                              (oz/cwt)                                                                              (oz/cwt) (oz/cwt)  incognita                                                                            christiei                                                                            phagus                               ______________________________________                                        Control --       --        221    30     55                                   (untreated)                                                                   16      3.3      0         146    3      14                                   16      3.3      3.3       62     2      8                                    24      3.3      0         69     7      1                                    24      3.3      3.3       57     2      10                                   32      3.3      0         86     1      2                                    32      3.3      3.3       44     1      1                                    ______________________________________                                    

The results from Table X illustrate a significant reduction of allnematode species in wheat root systems from thiodicarb treated wheatseeds in comparison with wheat root systems grown from untreated wheatseeds.

It will be understood that the nematode species employed in the abovetests are merely representative of a wide variety of nematodes that canbe controlled by he suIfur-oontaining compounds represented by thegeneric formula 1.

Although the invention has been illustrated by the preceeding examples,it is not to be construed as being limited thereby; but rather, theinvention enoompasses the generic area as hereinbefore disclosed.Various modifications and embodiments can be made without departing fromthe spirit and scope thereof.

We claim:
 1. A method of protecting plants from plant parasiticnematodes comprising applying to the locus of nematode infestation aplant protectant amount of a compound having the formula: ##STR23##wherein: R₁₄ and R₁₅ are independently alkyl radicals having from 1 to 4carbon atoms;R₁₆ is tetrahydronaphthyl, naphthyl, benzothienyl,dihydrobenzofuranyl, benzofuranyl or: ##STR24## R₁₇ is other than R₁₆and is a substituted or unsubstituted alkyl, cycloalkyl, phenylalkyl,naphthylalkyl or a heterocycloalkyl group, wherein the heterocyclicmoiety is a five-or six-member ring which includes in any combination,one or two oxygen, sulfur, sulfinyl or sulfonyl groups and which mayalso include one divalent, amino, alkylamino or carbonyl group; whereinthe permissible substituents on said groups are one or more halogen,nitrile, nitro, alkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy,alkoxycarbonylamino, or alkylcarbonylamino groups in any combination, orR₁₇ is alkoxyalkyleneoxyalkyl, alkoxy(dialkyleneoxy)alkyl oralkoxy-(trialkyleneoxy)alkyl; R₁₈ is hydrogen, alkyl, alkylthio orcyano; R₁₉ is alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, allof which may be unsubstituted or aliphatically substituted in anycombination with one or more cyano, nitro, alkylthio, alkylsulfinyl,alkylsulfonyl, alkoxy, aminocarbonyl, alkylaminocarbonyl, ordialkylaminocarbonyl groups; or R₁₉ is phenyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl or a R₂₄ CONH-- or R₂₄CON(alkyl)-- group, where R₂₄ is hydrogen, alkyl, alkoxy or alkylthio;and A₁ is a divalent aliphatic chain, completing a five or six memberring, which includes in any combination, one or two oxygen, sulfur,sulfinyl or sulfonyl groups and which may also include one divalentamino, alkylamino or carbonyl group; R₂₀ is alkoxy, alkylthio, alkyl,alkylthioalkyl 2-dioxalanyl, 2-dithioanyl, 2-oxathioanyl, substitutedalkoxy in which the permissible substituents are alkoxy and haloalkyl inany combination, or halogen; R₂₁ is alkyl; R₂₂ is hydrogen, alkyl,halogen, alkylthio, alkysulfinyl, alkylsulfonyl, alkoxy, dialkylamino,formylamino, alkylcarbonylamino, alkoxycarbonylamino ordialkylaminomethyleneimino; and R₂₃ is hydrogen or alkyl.
 2. A method ofprotecting plants from plant parasitic nematodes comprising applying tothe locus of nematode infestation a plant protectant amount of acompound having the formula: ##STR25## wherein: R₂₅ and R₂₆ areindividually alkyl radicals having from 1 to 4 carbon atoms;R₂₇ is##STR26## R₂₇ is alkynyl; R₂₈ is other than R₂₇ and is alkenyl, alkynyl,phenyl, benzofuranyl, dihydrobenzofuranyl, benzothienyl, naphthyl ortetrahydronaphthyl all of which may be either unsubstituted orsubstituted with one or more halogen, nitro, nitrile, alkyl, alkylthio,alkylthioalkyl, methylenedioxy, amino, alkylamino, dialkylamino,alkoxycarbonylamino, dialkylaminoalkyleneimino, alkylcarbonylamino,formylamino, dicyanoethylidene, alkoxy, alkynyloxy, phenoxy, phenyl,2-dithianyl, 2-dithiolanyl, 2-dioxalanyl, 2-oxathianyl, 2-oxathiolanyl,2-dioxanyl or 4-oximino-1,3-dithiolanyl groups in any combination; orR₂₈ is: ##STR27## wherein: R₂₉ is hydrogen, alkyl, alkylthio orcyano;R₃₀ is alkyl, alkylthio, alkylthioalkyl, alkoxy, aroyl, alkanoylor alkoxycarbonyl, all of which may be unsubstituted or aliphaticallysubstituted in any combination with one or more cyano, nitro, alkylthio,alkylsulfinyl, alkylsulfonyl, alkoxy, aminocarbonyl,dialkylaminocarbonyl or alkylaminocarbonyl groups; or R₃₀ is phenyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or an R₃₁ CONH--or R₃₁ CON(alkyl)group where R₃₁ is hydrogen, alkyl or alkoxy; and A₂ isa divalent aliphatic chain, completing a five or six member ring, whichincludes one or two divalent oxygen, sulfur, sulfinyl or sulfonyl groupsand which may also include one divalent amino, alkylamino or carbonylgroup in any combination; or A, may also complete a six membered ringwhich includes three divalent sulfur, sulfinyl or sulfonyl groups in anycombination.
 3. A method of protecting plants from plant parasiticnematodes comprising applying to the locus of nematode infestation aplant protectant amount of a compound having the formula: ##STR28##wherein: R₃₂ is hydrogen, alkyl, alkenyl, alkoxy, or cycloalkyl, eitherunsubstituted or except where R₃₂ is hydrogen, substituted with one ormore chloro, bromo, fluoro, nitro or cyano substitutents in anycombination, or phenyl or phenylalkyl, either unsubstituted orsubstituted with one or more chloro, bromo, fluoro, nitro, cyano, alkyl,haloalkyl or alkoxy substitutents in any combination:R₃₄ is ##STR29##wherein: R₃₅ and R₃₆ are individually hydrogen, alkyl, alkenyl, alkoxy,cycloalkyl, phenylalkyl or phenyl, all of which may be unsubstituted orsubstituted, except in the case of hydrogen, with one or more chloro,bromo, fluoro, nitro, cyano, alkyl, haloalkyl, or alkoxy substituents inany combination; or a saturated or unsaturated five or six memberedheterocyclic radical in which there are one or two hetero atoms whichmay be oxygen, sulfur in all of its oxidation states or nitrogen,including combinations thereof, all of which heterocyclic radicals maybe unsubstituted or substituted with one or more chloro, bromo, fluoro,nitro, cyano, alkyl, haloalkyl, or alkoxy substituents in anycombination:A₃ is a divalent aliphatic chain which may be alkylene,alkenylene or an aliphatic chain which may include one or two heteroatoms of oxygen, sulfur in all of its oxidation states or nitrogen or acombination thereof to form a five or six membered ring structure, whichmay be unsubstituted or substituted with one or more chloro, bromo,fluoro, nitro, cyano, alkyl, haloalkyl or alkoxy substituents in anycombination: R₃₃ is an imino group of the formula: ##STR30## wherein:R₃₇ and R₃₈ are individually hydrogen, cyano or chloro radicals or arealkyl, alkenyl, alkylthio, alkoxy, aryl, arylthio, carbamoyl,aminocarbonylalkyl or carbonylaminoalkyl groups or are joined togetherby a saturated or unsaturated divalent aliphatic chain which may beinterrupted by one or more sulfur in all of its oxidation states, oxygenor nitrogen atoms to form a five or six membered ring all of which maybe substituted by one or more chloro, bromo, fluoro, nitro, cyano,alkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, or alkoxy substituentsin any combination.
 4. A method of protecting plants from plantparasitic nematodes comprising applying to the locus of nematodeinfestation a plant protectant amount of a compound having the formula:##STR31## wherein: R₃₉, R₄₀ and R₄₁ are independently alkyl having from1 to 8 carbon atoms; andR₄₂ is independently alkylthio, alkylsulfinyl,alkylsulfonyl or alkylthioalkyl.
 5. A method of protecting plants fromplant parasitic nematodes comprising applying to the locus of nematodeinfestation a plant protectant amount of a compound having the formula:##STR32## wherein: R₄₃ is:A. a substituted or unsubstituted divalentalkylene, alkenylene, alkynylene, monocyclic arylene, bicyclic arylene,biphenylene or a divalent alkylene chain which includes one oxygen,sulfur, sulfinyl, sulfonyl or nitrogen, wherein the permissiblesubstituents are one or more alkyl, fluoro, nitro, chloro or bromogroups in any combination: or B. A divalent organic radical of theformula: ##STR33## wherein: Y is oxygen, sulfur, sulfinyl, sulfonyl,alkylene, haloalkylene. alkenylene or haloalkenylene: R₄₄, R₄₅, R₄₆ andR₄₇ are independently alkyl having from one to four carbon atoms; R₄₈is:A. dihydrobenzofuranyl, naphthyl, tetrahydronaphthyl, benzothienyl,indanyl, benzodioxalanyl, benzofuranyl or benzodioxanyl groups, all ofwhich may be either unsubstituted or substituted with one or more alkylgroups in any combination: or B. phenyl, either unsubstituted orsubstituted with one or more halo, cyano, nitro, cycloalkyl, alkyl,alkylthio, alkylsulfinyl 2-dithiolanyl, alkylsulfonyl, alkylthioalkyl,alkylsulfinylalkyl, 2-dioxalanyl, alkylsulfonylalkyl, amino, alkylamino,dialkylamino, alkynyloxy, alkoxycarbonylamino, trihalomethyl, N,N-dialkylformamidino, or alkoxy in any combination; or C. ##STR34##wherein: R₄₉ is hydrogen, alkyl, alkylthio, alkylsulfinyl,alkylsulfonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonylor cyano;R₅₀ is alkyl, alkylthio, alkylsulfinyl, alkylsulfonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or alkanoyl, allof which may be unsubstituted or, except for aminocarbonyl, substitutedwith one or more cyano, amido, nitro, alkylthio, alkylsulfonyl oralkylsulfinyl in any combination; and A₄ is a divalent alkylene chainhaving from 2 to 24 aliphatic carbon atoms completing a five or sixmembered ring structure which includes one, two or three groups selectedfrom divalent oxygen, sulfur, sulfinyl, sulfonyl, amino, alkylamino,alkylimino or carbonyl groups in any combination.
 6. A method ofprotecting plants from plant parasitic nematodes comprising applying tothe locus of nematode infestation a plant protectant amount of acompound having the formula: ##STR35## wherein: R₅₁ and R₅₂ areindependently alkyl having from 1 to 4 carbon atoms;R₅₃ is: ##STR36##wherein: R₅₄ is hydrogen, chloro, cyano, alkyl, alkylthio orcyanoalkylthio;R₅₅ is alkyl, alkylthio, alkoxy, alkanoyl, benzoyl,alkoxycarbonyl, alkylsulfonyl, alkylsulfinyl, alkenyl, alkynyl orphenyl, all of which may be substituted in any combination with one ormore cyano, nitro, fluoro, bromo, chloro, alkylthio, alkylsulfinyl,alkylsulfony, alkoxy, phenoxy, carbamoyl, alkylcarbamoyl,dialkylcarbamoyl or ##STR37## wherein: R₅₆ is hydrogen or alkyl;R₅₇ ishydrogen, alkyl, alkoxy or alkylthio; and A₅ is a divalent alkylenechain having from 2 to 24 aliphatic carbon atoms completing a five orsix membered alicyclic ring which includes one, two or three groupsselected from divalent oxygen, sulfur, sulfinyl, sulfonyl, amino,alkylamino, alkylimino or carbonyl groups in any combination.
 7. Amethod of protecting plants from plant parasitic nematodes comprisingapplying to the locus of nematode infestation a plant protectant amountof a compound having the formula: ##STR38## wherein R₅₈ is selected from##STR39## wherein R₆₀, R₆₁ and R₆₂ are the same or different and arehydrogen, alkylyn, halogen, alkoxy, alkylthio, dialkylamino or--N═CHN(CH₃)₂ ; ##STR40## wherein B₁ and B₂ are the same or differentand are alkyl, alkylthio, monocyano substituted alkylthio, phenylthiowherein phenyl may be unsubstituted or substituted with one or moresubstituents which may be the same or different and are halogen, alkyl,cyano, alkoxy, phenyl and hydrogen, with the proviso that when B₁ ishydrogen, then B₂ is of the formula ##STR41## wherein R₆₃ is alkyl orphenyl; R₆₄ is alkyl; R₆₅ is alkyl or SR₆₆, wherein R₆₆ is alkyl and isthe same alkyl group as R₆₃, and taking R₆₃ and R₆₆ together with theatoms to which they are attached may form a dithio heterocyclic of theformula ##STR42## wherein q is 2 or 3 and the alkylene portion of thering is unsubstituted or substituted with one or two methyl groups; B₁and B₂ taken together with the carbon atom to which they are attachedmay form a dithio heterocyclic of the formula ##STR43## wherein thealkylene portion of the ring is unsubstituted or substituted with one totwo methyl groups; and ##STR44## R₅₉ is alkyl, phenyl, substitutedphenyl, phenyl-alkyl, and cycloalkyl; X is oxygen or sulfur; Y₁ and Y₂are the same or different and are alkyl, alkoxy, alkylthio, cycloalkyl,phenyl, substituted phenyl, phenoxy, substituted phenoxy, thiophenoxy,and substituted thiophenoxy; Z₁ through Z₆ are the same or different andare hydrogen, methyl and ethyl; k is zero or one, p is three or four;and R₆₇ is hydrogen, alkyl, alkoxy and halogen.
 8. A method ofprotecting plants from plant parasitic nematodes comprising applying tothe locus of nematode infestation a plant protectant amount of acompound having the formula: ##STR45## wherein R₆₈ is ##STR46## and R₆₉and R₇₀ are the same or different and are alkyl, cycloalkyl, benzylwhich is unsubstituted or substituted with halogen, alkyl or alkoxy inany combination, phenyl which is unsubstituted or substituted withhalogen. alkyl or alkoxy, --X₁ --COOR₇₁ or --Y₃ --CN in any combinationin which X₁ and Y₃ are each straight-chain or branched-chain alkyleneand R₇₁ is alkyl or cycloalkyl, or R₆₉ and R₇₀, when taken together, mayrepresent a 5- or 6-membered heterocyclic ring which may contain asulphur or oxygen atom.
 9. A method of protecting plants from plantparasitic nematodes comprising applying to the locus of the nematodeinfestation a plant protectant amount of a compound having the formula:##STR47## wherein R₇₂ is ##STR48## wherein: R₇₃ and R₇₄ areindependently --X₂ --COOR₇₅, or --Y₄ --CN;X₂ and Y₄ are independentlyalkylene; R₇₅ is alkyl or cycloalkyl; or R₇₄ is alkyl, cycloalkyl,alkoxyalkyl, unsubstituted or substituted phenyl in which thepermissible substitutents are halogen, alkyl or alkoxy in anycombination, unsubstituted or substituted benzyl in which thepermissible substituents are halogen, alkyl or alkoxy in any combinationor --Z₇ --R₇₆ ; Z₇ is carbonyl or sulphony; R₇₆ is alkyl, alkoxy,phenoxy, or unsubstituted or substituted phenyl in which the permissiblesubstituent is alkyl in any combination.
 10. A method of protectingplants from plant parasitic nematodes comprising applying to the locusof the nematode infestation a plant protectant amount of a compoundhaving the formula: ##STR49## wherein: R₆ and R₇ are the same and are:##STR50## wherein: R₁₀ is alkyl, alkylthio, alkoxy, alkanoyl oralkoxycarbonyl, all of whiCh may be unsubstituted or aliphaticallysubstituted in any combination with one or more cyano, nitro, alkylthio,alkylsulfinyl, alkysulfonyl, alkoxy or R₁₂ R₁₃ --NCO-- groups; or R₁₀ isphenyl, R₁₂ R₁₃ NCO-- or R₁₂ CON(R₁₃)--;wherein: R₁₂ and R₁₃ areindependently hydrogen, alkyl or alkoxy; R₁₁ is hydrogen, alkyl,alkylthio or cyano; A is a four- or five-member divalent aliphatic chainwhich includes one or two divalent oxygen, sulfur, sulfinyl or sulfonylgroups and which may include not more than one divalent amino,alkylamino or carbonyl groups, in any combination; and R₈ and R₉ areindependently alkyl containing from one to four carbon atoms.
 11. Amethod of protecting plants from plant parasitic nematodes comprisingapplying to the locus of the nematode infestation a plant protectantamount of a compound having the formula: ##STR51## wherein: R₇₉ and R₈₀are independently a hydrocarbyl group containing from 1 to 12 carbonatoms; R₇₇ is a hydrocarbyl group containing from 1 to 20 carbon atoms,a 5 to 6 membered heterocyclic ring containing O or S atoms, or a >C═N--radical; and R₇₈ can be other than R₇₇ and is a hydrocarbyl groupcontaining from 1 to 20 carbon atoms or a 5 to 6 membered heterocyclicring containing O or S atoms; or R₇₈ can be the same as R₇₇.
 12. Amethod of protecting plants from plant parasitic nematodes comprisingapplying to the locus of the nematode infestation a plant protectantamount of a compound having the formula: ##STR52## wherein: R₈₁ is alkylof 1 to 4 carbon atoms; R₈₂ is a heterocyclic group of the formula:##STR53## in which R₈₆ and R₈₇ are hydrogen or alkyl of 1 to 4 carbonatoms, A₆ and B₁ are each oxygen, or one of A₆ and B₁ is methylene andthe other is oxygen or sulfur; or R₈₂ is an imino group of the formula##STR54## wherein R₈₈ is hydrogen, a dialkylaminocarbonyl or alkyl of 1to 4 carbon atoms and R₈₉ is alkylthio or alkylthioalkyl and wherein thealkyl groups are the same or different and have 1 to 4 carbon atoms;R₈₃is alkyl of 1 to 12 carbon atoms; or cycloalkyl of 3 to 6 carbon atoms;X₃ is oxygen or sulfur; and R₈₄ and R₈₅ are the same or different andare alkyl of 1 to 6 carbon atoms; or together can constitute the carbonsnecessary to complete a 5 to 6 membered ring system which is eitherunsubstituted or substituted by 1 or 2 methyl groups.
 13. A method ofprotecting plants from plant parasitic nematodes comprising applying tothe locus of the nematode infestation a plant protectant amount of acompound having the formula: ##STR55## wherein R₉₀ and R₉₁ may be thesame or different and are alkyl of 1 to 8 carbon atoms, cycloalkyl of 3to 6 carbon atoms, or benzyl, or R₉₀ and R₉₁ taken together with thenitrogen may form a pyrollidine, piperidine, morpholine, piperazine, orhexahydroazepine heterocyclic ring which may have one or moresubstituents selected from alkyl, benzyl, phenyl, or alkoxy.
 14. Amethod of protecting plants from plant parasitic nematodes comprisingapplying to the locus of the nematode infestation a plant protectantamount of a compound having the formula: ##STR56## wherein: R₉₂ and R₉₃individually are hydrogen or alkyl of 1 to 4 carbon atoms, and R₉₄ isalkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms,monocyclic or bicyclic aryl of 6 to 10 carbon atoms, alkyl of 2 to 12carbon atoms substituted with 1 to 5 flourine, chlorine or bromineatoms, alkenyl of 2 to 12 carbon atoms substituted with 1 to 5 flourine,chlorine or bromine atoms, or monocyclic or bicyclic aryl of 6 to 10carbon atoms substituted with 1 to 5 flourine, chlorine or bromineatoms, or 1 to 2 nitro groups.
 15. A method of protecting plants fromplant parasitic nematodes comprising applying to the locus of thenematode infestation a plant protectant amount of a compound having theformula: ##STR57## wherein: R₉₅ is C₁ -C₁₀ alkyl, C₁ -C₂ alkoxy-C₁ -C₂alkyl or cyclohexyl and R₉₆ is C₁ -C₄ alkyl.
 16. A method of protectingplants from plant parasitic nematodes comprising applying to the locusof the nematode infestation a plant protectant amount of a compoundhaving a formula selected from the group consisting of: ##STR58## 17.The method of claim 16 wherein the compound has the formula ##STR59##18. The method of claim 16 wherein the compound has the formula##STR60##
 19. The method of claim 16 wherein the compound has theformula ##STR61##
 20. The method of claim 16 wherein the compound hasthe formula ##STR62##
 21. The method of claim 16 wherein the compoundhas the formula ##STR63##
 22. The method of claim 16 wherein thecompound has the formula ##STR64##
 23. The method of claim 16 whereinthe compound has the formula ##STR65##
 24. The method of claim 16wherein the compound has the formula ##STR66##
 25. The method of claim16 wherein the compound has the formula ##STR67##
 26. The method ofclaim 16 wherein the compound has the formula ##STR68##
 27. The methodof claim 16 wherein the compound has the formula ##STR69##
 28. Themethod of claim 16 wherein the compound has the formula ##STR70## 29.The method of claim 16 wherein the compound has the formula: ##STR71##30. The method of claim 1 wherein the compound is applied to a plantseed.
 31. The method of claim 1 wherein the compound is applied to aplant seed piece.
 32. The method of claim 1 wherein the compound isapplied to a plant root system.
 33. The method of claim 1 wherein thecompound is applied to a plant seed or seed piece at a concentration offrom about 0.1 to about 10 percent by weight of the total weight of theseed or seed piece.
 34. The method of claim 1 wherein the compound isapplied to a plant root system or seed piece at a concentration of fromabout 0.001 to about 10 percent by weight of the total weight of theplant root system or seed piece.
 35. The method of claim 1 in which thecompound is used in combination with one or more biologically activematerials.